JP6923536B2 - Molecules with pesticide utility and related intermediates, compositions and processes - Google Patents

Description

Cross-reference to related applications This application claims the interests and priorities of US Provisional Patent Applications 62/286631 and 62/286642 filed on January 25, 2016, which are references. Explicitly incorporated herein by.

The present disclosure describes molecules that have pesticide efficacy against pests of the phylum Arthropod, Pyramid phylum, and phylum Linear phylum, the process of producing such molecules, the intermediates used in such processes, and such molecules. The present invention relates to a pesticide composition containing, and a field relating to the process of using the pesticide composition against such pests. These pesticide compositions can be used, for example, as acaricides, insecticides, acaricides, mollusk repellents, and nematodes.

"Many of the most dangerous human diseases are transmitted by vector insects" (Rivero et al.). "Historically, malaria, dengue, yellow fever, pesto, filariasis, typhus, typanomiasis, leishmaniasis, and other arthropod-borne diseases were found in the 17th and early 20th centuries. , The cause of human disease and death was more than the sum of all other causes "(Gubler). Arthropod-borne diseases account for about 17% of the world's parasites and infectious diseases. Malaria alone causes more than 800,000 deaths a year, 85% of which affect children under the age of five. There are about 50 to 100 million cases of dengue fever annually. In addition, 250,000 to 500,000 cases of dengue hemorrhagic fever occur annually (Matthews). Vector animal control plays a decisive role in the prevention and control of infectious diseases. However, pesticide resistance, including resistance to multiple pesticides, has occurred in all insect species that are the major vectors of human disease (Rivero et al.). Recently, more than 550 arthropod pest species have become resistant to at least one pesticide (Whalon et al.).

Every year, insects, phytopathogens and weeds ruin more than 40% of total food production. This loss occurs despite the application of pesticides and the use of various non-chemical controls such as crop rotation and biological control. If only some of these foods could be saved, they could be used to feed more than 3 billion malnourished people worldwide (Pimental).

Plant-parasitic nematodes are one of the most widespread pests and often one of the most insidious and costly. Losses due to nematodes have been estimated to range from about 9% (developed countries) to about 15% (developing countries). However, in the United States, a survey of 35 states on various crops revealed that nematode-induced losses amounted to as much as 25% (Nicol et al.).

Pests (slugs and snails) are less economically important pests than other arthropods or nematodes, but in certain places they substantially reduce yields and significantly affect crop quality. It can also transmit human and animal diseases and plant diseases. Dozens of abalone are serious regional pests, and several are the major pests on a global scale. In particular, abalone affects a wide range of crops and horticultural crops such as cultivated crops, livestock crops, and fiber crops; vegetables; fruit trees; herbs; and ornamental plants (Spieser).

Termites cause damage to all types of private and public buildings, as well as agricultural and forestry resources. In 2005, termites were estimated to cause US $ 50 billion annually in damage worldwide (Korb).

Therefore, it is costly (estimated at about US $ 256 million per pesticide in 2010), time consuming (on average about 10 years per pesticide), for many reasons, including those mentioned above. In addition, the development of new pesticides, which is difficult, is continuously required (CropLife America).

DeMassey et al. Disclose the following structure. See US2002 / 0068838 for more details.

Specific references cited in this disclosure, CropLife America, The Cost of New Organic Product Discovery, Development & Regency, and Research & Development.
Gubler, D.M. , Resurgent Vector-Bone Diseases as a Global Health Problem, Emerging Infectious Diseases, Vol. 4, No. 3, p. 442-450, 1998.
Kobe, J. et al. , Termites, Current Biology, Vol. 17, No. 23,2007.
Matthews, G.M. , Integrated Vector Management: Controlling Vectors of Malaria and Other Insect Vector Borne Diseases, Ch. 1, p. 1-2011.
Nicol, J. et al. , Turner S.A. Coyne, L. et al. Den Nijs, L .; , Hocksland, L .; , Tahna-Maafi, Z. et al. , Current Nematode Threats to World Agriculture, Genomic and Molecular Genetics of Plant-Nematode Interactions, p. 21-43, 2011).
Basical, D.I. , Pest Control in World Agriculture, Agricultural Sciences-Vol. II, 2009.
Rivero, A. et al. , Veziier, J. Mol. , Will, M. et al. , Read, A. , Gandon, S.A. , Insect Control of Vector-Bone Diseases: When is Insect Response a Problem? Public Library of Science Pathogens, Vol. 6, No. 8, p. 1-9, 2010.
Speaker, B.I. , Molluscides, Encyclopedia of Pest Control, Ch. 219, p. 506-508, 2002.
Wholon, M. et al. , Mota-Sanchez, D.M. , Hollingworth, R.M. , Analysis of Global Pestistence in Analysis, Analysis of Global Pestistence in Analysis, Ch. 1, p. 5-33,2008.

Definitions used in this disclosure The examples presented in this definition are generally non-exhaustive and should not be construed as limiting this disclosure. It is understood that the substituent should comply with the chemical bonding rules and steric compatibility restrictions for the particular molecule to which it binds. These definitions are used solely for the purposes of this disclosure.

"Active ingredient" means a substance having an activity useful for controlling pests and / or a substance useful for assisting another substance having an excellent activity for controlling pests, and is limited as an example of such a substance. Not done, but acaricide, algae, bird killer, bactericide, fungicide, herbicide, pesticide, rodenticide, rodenticide, rodenticide, virus killing agent, feeding inhibitor, bird Included are repellents, chemical fertilizers, herbicides, toxicity mitigators, insect attractants, insect repellents, mammalian repellents, mating inhibitors, plant activators, plant growth regulators, and synergists. Specific examples of such substances include, but are not limited to, the substances listed in the active ingredient group alpha.

本明細書では、使用の容易さを目的として、本分子を「ＡＩ−１」と名付ける。
（３） 以下の構造を有するロチラネル（Ｌｏｔｉｌａｎｅｒ）として知られる分子

；及び
（４） 表Ａに記載の以下の分子
表Ａ−Ｍの構造−活性成分

本開示で使用される場合、上記の各々が活性成分であり、および２個以上が活性成分である。詳しい情報については、「Ｔｈｅ Ｐｅｓｔｉｃｉｄｅ Ｍａｎｕａｌ」のオンライン版（ｂｃｐｃｄａｔａ．ｃｏｍに記載）をはじめとする、「Ｃｏｍｐｅｎｄｉｕｍ ｏｆ Ｐｅｓｔｉｃｉｄｅ Ｃｏｍｍｏｎ Ｎａｍｅｓ」（Ａｌａｎｗｏｏｄ．ｎｅｔおよび諸版に記載）を参照されたい。

"Active ingredient group alpha" (hereinafter "AIGA") collectively means the following substances:
(1) (3-ethoxypropyl) mercury bromide, 1,2-dibromoethane, 1,2-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropene, 1-MCP, 1-methylcyclopropene, 1-naphthol, 2- (octylthio) ethanol, 2,3,3-TPA, 2,3,5-tri-iodobenzoic acid, 2,3,6-TBA, 2,4,5-T, 2,4 , 5-TB, 2,4,5-TP, 2,4-D, 2,4-DB, 2,4-DEB, 2,4-DEP, 2,4-DES, 2,4-DP, 2 , 4-MCPA, 2,4-MCPB, 2iP, 2-methoxymethylmercuric chloride, 2-phenylphenol, 3,4-DA, 3,4-DB, 3,4-DP, 3,6-dichloropicolinic acid, 4-Aminopyridine, 4-CPA, 4-CPB, 4-CPP, 4-Hydroxyphenyl alcohol, 8-hydroxyquinoline sulfate, 8-phenylmercuryoxyquinoline, abamectin, abamectin-aminomethyl, absicic acid, ACC, acetylate. , Acequinosyl, acetamipride, acethion, acetochlor, acetophenate, acetophos, acetoprol, acibenzoral, asifluorphen, acronifen, ACN, acrep, acrinatrin, achlorine, acrylonitrile, acipetax, afidopyropen, ahoxolana, alacrol, alanap Albendazole, aldicalve, aldicalb sulfone, aldimorph, aldoxycarb, aldrin, alesulin, alicin, allydocrol, allosamidin, aloxidim, allylalcohol, alixylve, allolac, α-cypermethrin, α-endosulfane, alphamethrin, altretamine, Aluminum Phosphate, Aluminum Phosphate, Amethcladine, Ametridione, Amethrin, Amethrine, Amibudin, Amicabazole, Amicartiazole, Amidithion, Azidoflumeth, Amidosulfuron, Aminocarb, Aminocyclopyracrol, Aminopyralid, Aminotriazol -Methyl, amiprophos, amiprophos-methyl, amisulfome, amitone, amitraz, amitrol, ammonium sulfamate, amovam, amorphous silica gel, amorphous silicon dioxide, ampropifphos, AMS, anabacin, ansimidol, anila Zin, anilophos, anislon, anthraquinone, anz, aholate, alamite, alprocarb, arsenic trioxide, asomet, aspirin, aslam, atidathione, atlaston, atlasin, aureofungin, avelmectin B1, AVG, abigricin, azaconazole, azaziractin. Azamethifos, azidithione, azisulfone, adihocetyl, azinephos-ethyl, azinephosmethyl, azinephos-methyl, adiprothrin, adiprothrin, azitiram, azobenzene, azocyclotin, azotoate, azoxystrobin, bakumedesh, balban, barbanate, barium hexafluoride , Barium polysulfide, barium silicate, baltrin, basic copper carbonate, basic copper chloride, basic copper sulfate, BCPC, beflubutamide, benaraxyl, benaraxyl-M, benazolline, bencarbazone, bencrothias, bendakingbingji, benziocarb, benzy Oxide, benefin, benfluthrin, benfracarb, benfresate, benmifangkaoan, benodanyl, benomil, benoxacol, benoxaphos, benquinox, bensulfuron, benslide, bensultap, ventallon, ventazone, ventazone, benchavaricarb , Benzadox, benzalkonium chloride, benzamacryl, benzamizole, benzamorph, benzenehexachloride, benzfendizone, benzimine, benziplum, benzobicyclon, benzoepine, benzofanap, benzofluore, benzohydroxamic acid, benzomate, benzophosphate, benzothiazole, benzo Bingiflupill, benzoximate, benzoylprop, benzthiazulone, benzokaotong, benzyl benzoate, benzyladenine, velverin, β-cyfluthrin, β-cypermethrin, betoxazine, BHC, bialaphos, bicyclopyrone, biphenazeto, biphenox, biphenthrin, Bifujunji, Vilanaphos, Vinapacryl, Bintinsiao, Bioaletrin, Bioetanomethrin, Biopermethrin, Bioresmethrin, Biphenyl, Bisazil, Bismerthiazole, Bismerthiazole-Copper, Bisphenylmercury methylenedi (x-naphthalen-y-sulfonate), Bispyribac, Bistriflulon, Bisultap, Bitel Tanol, bithionol, bixaphen, blasticidin-S, boric acid, Bordeaux solution, boric acid, boscalide, BPPS, brushnolide, brushnolide-ethyl, brevicomine, brodifacomum, brophenoplox, brofenvalerate, brofanilide, brofluthrinete, bromacil, bromazilone , Bromclophos, brometalin, bromesulin, bromfenbinphos, bromoacetamide, bromobonil, bromobutide, bromocylene, bromocyclen, bromo-DDT, bromophenoxym, bromophos, bromomwrn, bromophos, bromophos-ethyl Rate, bromotalonil, bromoxinyl, brompyrazone, bromconazole, bronopol, BRP, BTH, bucarporate, bufencarb, buminaphos, bupilimate, buprofezin, bordeaux solution, busulfan, busulfan, busulfan, butacarb, butachlor Butane-fipronil, butatiophos, butenachlor, butene-fipronil, butetrin, butidazole, butiobate, butiuron, butyphos, butocarboxym, butonate, butopyronoxyl, butoxycarboxym, butrulin, butridine, butoroxydim, butulamine, butyrate, butylchlorophos, Butylene-fipronil, cacodylate, cadeyusaphos, cafentrol, calciferol, calcium arsenate, calcium chlorate, calcium cyanamide, calcium cyanide, calcium polysulfide, carbinophos, cambendichlor, camfechlor, camphor, captahole, captan, carbam , Carbamorph, carbarolate, carbaryl, carbaryl, carbaslam, carbathione, carbendazim, carbendersol, carbetamid, carbophenothione, carbofuran, carbon disulfide, carbon tetrachloride, carbonyl sulfide, carbophenothione, carbophos, Carbosulfane, Carboxazole, Carboxido, Carboxin, Calfentrazone, Calpropamide, Cartap, Carbaryl, Carboyl, CAVP, CDAA, CDEA, CDEC, Celocidin, CEPC, Ceralle, Serenox, Sevadilla , Chest Hunt Solution, Tinalphos, Tinalphos-Methyl, Chinometryat, Chinomethionate, Kiraraxil, Chitosan, Clobenazone, Clomethoxyphene, Chlorolose, Chloramben, Chloramine Phosphorus, Chloramphenicol, Chloraniforman, Chloranyl, Chloranokryl Chlorantraniliplol, Chlorazihop, Chlorazine, Chlorbenside, Chlorbenzurone, Chlorbicylene, Chlorbromron, Chlorbfam, Chlordan, Chlordecon, Chlordimeholm, Chlorlempentrin, Chlorethaseto, Chloretaseton, Chloroform Chloreturone, Chlorphenac, Chlorphenapir, Chlorphenazole, Florphenetol, Chlorphenidim, Chlorphenprop, Chlorfenson, Chlorphensulfide, Chlorfenbinphos, Chlorfenbinphos-methyl, Chlorfluazuron, Chlorfluazole , Chlorfluecol, Chlorflurene, Chlorfluenol, Chloridazone, Chlorimron, Chlorinate, Chlor-IPC, Chlormephos, Chlormequato, Chlormesron, Chlormethoxynyl, Chlornidin, Chlornitrophen, Chloroacetate, Chlorobenzylate, Chlorodinitronaphthalene, Chlorophenison, Chloroform, chloromebuform, chloromethiulone, chloroneb, chlorofacinone, chlorophos, chloropicrin, chloropon, chloropropilate, chlorotalonyl, chlorotorlon, chloroxifenidium, chloroxron, chloroxynyl, chlorhonium, chlorphoxim, chloroprazophos, chloroprocarb, chloroprofam, Chlorpyriphos, Chlorpyriphos-Methyl, Chlorquinox, Chlorsulfuron, Chlortal, Chlortiamide, Chlorthiophos, Chlortorlon, Closolinate, Kurtosan, Cholecalciferol, Choline Chloride, Chromaphenozide, Cycloheximide, Simectacarb, Cimetacarb, Cineline I, Cineline II, Cineline II Ethyl, symmethyrine, synosulfone, cintophen, siobutide, cisanilide, cismethrin, classifos, clefoxydim, clempirin, clenpyrin, cretojim, limbazole, chloroformate , Clozinahop, Chloetocarb, Crophenceto, Clophenotan, Clofentedin, Clofenbinfoss, Clofibric acid, Clohop, Chromazone, Chromeprop, Chronitralide, Cloprop, Chloproxim, Clopyralid, Croquintoset, Chloranthrum, Crosantel, Crotianidin, Closant. Trimazole, cloxyphonac, cloxylacon, clodilacon, CMA, CMMP, CMP, CMU, cordrelua, cholecalciferol, colohonate, copper-8-quinolinolate, copper acetate, copper acetohydrate, copper arsenate, basic copper carbonate, water Copper oxide, copper naphthenate, copper oleate, basic copper chloride, copper silicate, copper sulfate, basic copper sulfate, zinc copper chromate, coumacrol, kumafen, kumafos, kumafuryl, kumaphos, kumatetralyl , Cumethoxystrobin, cumitoate, spumoxystrobin, CPMC, CPMF, CPPC, credazine, cresol, cresylic acid, crimidin, crotamitone, crotoxyphos, crotoxyphos, kuhomet, cryolite, culua, kufuraneb , Cumylron, cuprovam, cuprous oxide, curcumenol, CVMP, cyanamide, cyanatrin, cyanazine, cyanophenphos, cyan, cyanophos, cyanotoate, cyantranliprol, cyanulic acid, siazofamide, cibutrin, cyclafuramide, cyclanilide, cyclaniliprol , Cycretoline, Cycloate, Licroheximide, Cycloplate, Cycloprothrin, Cyclopyrimolate, Cyclosulfamron, Cycloxidim, Cyclurone, Sienopyraphen, Siflufenamide, Siflumethofen, Siflutrin, Sihalohope, Sihalothrin, Sihexatin, Simiazol, Simoxanyl, Ciometrinyl Cipermethrin, Cipelcoat, Ciphenothrin, Cyprazine, Siprazole, Ciproconazole, Ciprodinyl, Ciprofulum, Cipromid, Ciprosulfamide, Siromadin, Cithioate, Citrex, Dimuron, Dalapon, Daminozide, Dayoton, Dazomet, DBCP, dd-Camper, DCB, DCIP, DCPA, DCPTA, DCU, DDD, DDPP, DDT, DDVP, Devacarb, Decafentin, Decamethrin, De Carbofuran, DEET, Dehydroacetic Acid, Diquat, Delacor, Delnab, Deltamethrin, Demefion, Demefion-O, Demefion-S, Demeton, Demeton-
Methyl, Demeton-O, Demeton-O-Methyl, Demeton-S, Demeton-S-Methyl, Demeton-S-Methyl Sulfone, Demeton-S-Methyl Sulfone, DEP, Deparetrin, Delice, Desmedifam , Desmethylin, desmethrine, d-fansilk Ebbingjuzuhi, diafentiurone, dialihol, dialiphos, diarate, diamidaphos, dianato, diatomaceous soil (diatomaceous earth) diatomite (diatomaceous earth) diatomite Dibutyl, dibutyl succinate, dicamba, dicapton, diclobenyl, diclofenthion, diclofluanide, dicron, dichloralurea, dichlorobenzulone, dichlorphenidim, dichlorfurrecole, dichlorofluenol, dichlormate, dichloromid, dichloromethane, dichloromeso Chiaz, dichlorophene, dichloroprop, dichloroprop-P, dichlorovos, dichlozolin, dichlozoline, diclobutrazole, diclosimet, diphrohop, dichromedin, dichloran, dicroslam, diclohole, diclofan, dichromol. Dicoumarol), Dicresyl, Diclotophos, Dikryl, Dikumarol, Dicyclanil, Dicyclonone, Dierdrine, Dienochlor, Dietamcoat, Dietatyl, Dietion, Dietithion, Dietionate, Dietofencarbate, Dietofencarbate , Diphenacomum, diphenoconazole, diphenopenten, diphenoxlon, diphenzoquat, difethialon, difluorovidazine, diphenopenten, diphenoxlon, diphenzoquat, difethialone, difluorovidazine, diflubenzlone, difluphenican, difluphenicanyl, difluphenicanyl Dikeglack, Dirol, Dimachif, Dimefluthrin, Dimefox, Dimeflon, Dimehipo, Dimepiperate, Dimethacron, Dimethane, Dimethacarb, Dimethacron, Dimethacrol, Dimethamethrin, Dimethenamide, Dimethenamide-P, Dimethypine, Dimethylimol Metoate, dimethomorph, dimethrin, dimethylcarbat, dimethyldisulfide, dimethylphthalate, dimethylbinphos, dimethylan, dimexano, dimidazone, dimoxystrobi, dipyrate, gymron, dinex, ginggenezuo, diniconazole, diniconazole-M, dinitramine, dinitrophenols , Dinocup, Dinocup, Dinocup-4, Dinocup-6, Dinoctone, Dinophenate, Dinopenton, Dinoprop, Dinosam, Dinoseb, Dinosulfone, Dinotefuran, Dinoseb, Dinotelbon, Diophenolan, Dioxabenzophos, Dioxacarb, Dioxation ), Difacin, difacinone, diphenadione, diphenamide, diphenamide, diphenylsulfone, diphenylamine, diphenylsulfide, diprogluic acid, diproparin, dipropetrin, dipterex, dipymethitron, dipyrityion, diquat Disparua, disgran, disul, disulfiram, dissulphoton, ditalimphos, dithianone, dithiclophos, dithioether, dithiomethon, dithiopyll, diuron, dixanthogen, d-limonene, DMDS, DMPA, DNOC, dodemorph, dodisin, dodin, dofenapin, doguadin Dramectin, DPC, dorazoxolone, DSMA, d-trans-allethrin, d-trans-resmethrin, zufurin, gymron, EBEP, EBP, ebphos, ecdysterone, ecromezol, EDB, EDC, EDDP, edifenphos, egrinadin, emamectin, EMPC, empentrin Enadenin, Endosulfan, Endothal, Endothal, Endothion, Endrin, Enestrovrin, Enilconazole, Enoxastrobin, Efilsulfonate, EPN, Epocholeon, Epophenonane, Epoxyconazole, Eprinomectin, Epironaz, EPTC , Elbon, Ergocalciferol, Elludixian Kaoan, Esdepalethrin, Esfenvalerate, ESP, Esprocarb, Etaceracil, Etaconazole, Etaphos, Etem, Etaboxam, Etachlor, Etalflularin, Etametosulfron, Etaprochlor, Etehon, Echidymron, Ethiophenalve, Ethiolate, Ethione, Ethiodin, Etiprol, Echimol, Etoate-methyl, Etobenzanide, Etophmesate, Etohexadiol, Etoprop, Etoprophos, ethoxyphen, ethoxykin Sulflon, ethyl chloride, ethyl formate, ethyl pyrophosphate, ethylan, ethyl-DDD, ethylene, ethylene dibromide, ethylene dichloride, ethylene oxide, etilicin, ethyl mercury 2,3-dihydroxypropyl mercaptide, ethyl mercury acetate, bromide Ethyl mercury, ethyl mercury chloride, ethyl mercury phosphate, ethinophene, ETM, etinopromid, etobenzanide, etofenprox, etoxazole, etridiazol, etrimphos, etrimphos, eugenol, EXD, famoxadon, famphosdon Phenaminosulf, Phenaminestrobin, Phenamiphos, Fenapanyl, Phenalimol, Phenaslam, Fenazaflor, Phenazakin, Fembuconazole, Fenbutatin Oxide, Fenchlorazole, Fenchlorphos, Phenoclophos, Fenchlorim, Fenetacarb, Fenfluthrin, Fenfuram, Fenhexa Mido, Phenidin, Fenitropan, Fenitrothione, Phenison, Fenjuntong, Phenoccarb, Phenorobo, Phenoprop, Phenothiocarb, Phenoxacrim, Phenoxanyl, Phenoxaprop, Phenoxaprop-P, Phenoxasulfone, Phenoxycarb, Fempicronyl, Fen Pyrythrin, fenpropatrin, fenpropidine, fenpropimorph, fenpyrazamine, fenpyroxamate, fenquinotrione, fenridazone, fenson, fensulfothione, fenteracol, fenthiaprop, fenthion, fenthion-ethyl, fenthiaprop, fentin , Fentrazamide, fentrifanyl, phenuron, phenuron-TCA, fenvalerate, fervum, ferimzone, ferric phosphate, iron sulfate, fipronil, flamprop, flamprop-M, frazasulfone, flokumaphen, fromotkin, fronicamid, floraslam , Full Acrypyrim, Full Ajihop, Fluazihop-P, fluazinum, fluazolate, fluazuron, flubenzidamide, flubenzimine, flubrocitrinate, flucarbazone, flucetosulfone, fluchloralin, flucofluone, flucycloxuron, flucitrinate, fludioxonyl, fluenetyl, fluenetyl Fluensulfone, flufenacet, fluphenerim, fluphenican, fluphenoxlon, fluphenoxystrobin, flufenprox, flufenpill, flufendin, flufiprol, fluhexaphone, flumethrin, flumethobel, flumethralin, flumethoslam, flumedin, flumicrolac, flumioxazine , Flumipropin, Flumorph, Fluometuron, Fluopicolid, Fluopirum, Fluolbenside, Fluolidamide, Fluoroacetamide, Fluoroacetic acid, Fluorochloridone, Fluorodiphen, Fluoroglycophen, Fluorimide, Fluoramide, Fluoromidin, Fluoronitrophen, Fluoroxypyr, Fluotyuron, fluotrimazole, fluoxastrobin, flupoxam, flupropasyl, flupropazine, flupropanate, flupyraziflon, flupyrusulfuron, fluconazole, flularanel, fluconazole, fluconazole, flurenol, flulidone, flulocrolidone, fluromidine, fluloxyl, fluluxyl Primidol, fluconazole, flurutamon, fluconazole, fluconulfamide, flutenzine, fluthiaset, fluthamide, flutianyl, flutranyl, flutriahole, fluvalinate, fluxapyroxado, fluxophenim, holpel, holpet, homesaphen, honofos, horamsflufuron, Holchlorphenuron, formaldehyde, formanate, formotione, formaparanate, hosamine, hosetil, phosmethylan, hospilate, hostiazet, hostietan, frontalin, phthalide, fluconazole, fluconazole, fukaomi, fujunmanti, fluconate, fumarin, funaihekaolin, ffenthiourea , Flametrin, Flametopil, Frantebphenozide, Frathiocarb, Fluconazole, Fluconazole, Fluconazole-cis, Fresulin, Furfural, Frilazole, Flumecyclo Cus, flufanate, friloxifene, γ-BHC, γ-cyhalothrin, γ-HCH, genit, dibereric acid, dibererin A3, dibererin, glyftor, glytor, glucochloralose, glufosinate, glufosinate-P, gliodine, glyoxime, glyphosate. , Glyphosin, Gosipurua, Grandlua, Glyceofrubin, Guanoctin, Guazatin, Halacrinate, Halauxifen, Halphenprox, Halofenozide, Halosaphen, Halothufflon, Haloxydin, Haloxyhop, Haloxyhop-P, Haloxyhop-R, HCA, HCB, HCH, Hemel, Hempa, HEOD, heptachlor, heptafluthrin, heptenophos, heptargil, harbimycin, harbimycin A, heterophos, hexachlor, hexachlorolane, hexachloroacetone, hexachlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexaflumron, hexa Fluolamine, hexaflulate, hekirua, hexamid, hexadinone, hexylthiophos, hexithiazox, HHDN, horosulf, homobrasnolide, fankaiwo, fanchontin, fankaolin, fanchunzo, hydramethylnone, hydrargafene, slaked lime , Hydrogen cyanide, hydrogen cyanide, hydroprene, hydroxyisoxazole, himexazole, hikincarb, IAA, IBA, IBP, icardine, imazaryl, imazamethabens, imazamox, imazapic, imazapill, imazakin, imazetapill, imazosulfuron , Iminoctadine, imiprothrin, inabenfide, indanophan, indaziflam, indoxacarb, inedin, drip soil, iodobonil, iodocarb, iodophenofus, iodomethane, iodosulfron, iofensulfone, ioxynyl, ipazine, IPC, ipconazole, ipencarba Zone, ipfentrifluconazole, iprogenphos, iprodione, iprovaricarb, iprimidum, ipsdienol, ipsenol, IPSP, IPX, isamidophos, isazophos, isobenzane, isocarbamide, isocarbamide, isocarbamide, isocarbamide, isocarbamide Isophenphos, isophenphos-methyl, isofetamide, isolane, isomethiodine, isonorlone, isopanphos, isopolynate, isoprocalve, isoprocyl, isopropalin, isopropazole, isoprothiolan, isoproturon, isopyrazam, isopyrylole, isothioate, isothienyl, isouron, isovalesion, isoxaben. Xachlortol, isoxadiphen, isoxaflutor, isoxapyrihop, isoxathione, islon, ibermectin, isoxaban, izopamphos, izopamphos, japonilua, japosulin, jasmorin I, jasmonic acid, jasmonic acid Zon, diazizenxiaolin, diatomaceous earth, diecaowan, diecaux, ginganmycin A, iodofenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III, cadesulin, κ-bifenthrin, κ-tefluthrin, carbutyrate , Caletazan, Kasgamycin, Kejunrin, Keleban, Ketospiradox, Diatomaceous earth, Kinetin, Kinoprene, Kiraraxil, Cresoxime-methyl, Quicaoxy, Lactophene, λ-Sihalosulin, Latilua, Lead arsenate, Lenacil, Repimectin, Leptofos, Lianbenzi Agents, Lindan, Lineatine, Linuron, Lilimhos, Littlea, Looplua, Lufenuron, Luxian Kaolin, Lubzing Junshi, Luvhumichuvzi, Luvsian Kaolin, Lithidathione, M-74, M-81, MAA, Magnesium phosphate, malathion, malathion, hydrazide maleate, malonoben, maltodextrin, MAMA, mancopper, mancozeb, mandestrobin, mandipropamide, maneb, matrin, majidox, MCC, MCP, MCPA, MCPA-thioethyl, MCPB, MCPP, Mebenil, Mecarbam, Mecalbindide, Mecalphone, Mecoprop, Mecoprop-P, Medimeform, Medinoterub, Medrua, Mefenacet, Mephenoxam, Mefenpil, Mefluidide, Megatomoic acid, Melicyl alcohol, Melitoxin, MEMC, Menazone, MEP, Mepanitel , Mepicat, Mepronil, Meptilzinocup, Mercaptodimetul, Mercap Tophos, mercaptophosthiol, mercaptothione, mercuric chloride, mercury oxide, mercuric chloride, merphos, merphos oxide, mesoprazine, mesosulfone, mesotrione, mesulfen, mesulfenphos, mesulfen, metacresol, metaflumison, metalaxyl, metalaxyl-M , Metaaldehyde, Metam, Metamihop, Metamitron, Metaphos, Metaxone, Metazachlor, Metazosulfone, Metazocosolone, Methoconazole, Metepa, Metofrazone, Metabenzthiazulone, Methachos, Metalpropalin, Metam, Metamidphos, Metasulfocarb, Metazol, Metofloxam , Methylbenzuron, methidathione, methionenecarb, methiocarb, methipylisulfuron, methiotepa, methiozoline, methiulone, methocrothos, methlucalve, methometon, methmil, methoprene, methoprotrin, methylmetholtine Methylphenozide, methoxyphenone, methylaphorate, methyl bromide, methyleugenol, methyl iodide, methylisothiocianate, methylpalathion, methylacetophos, methylchloroform, methyldithiocarbamic acid, methyldimron, methylene chloride, methyl-isophenphos, methylmercaptophos, Methyl mercaptophos oxide, Methyl mercaptophosthiol, Methyl mercury benzoate, Methyl mercury dicyandiamide, Methyl mercury pentachlorophenoxide, Methyl neodecanamid, Methyl nitrophos, Methyl triazothione, Methylozoline, Methylam, Methylam-zinc, Metbenzurone, Methylbromron, Metoflutrin, Methylchlor, Methylcarb, Methylmethurone, Methylminostrobin, Methyllam, Methyloxadiazone, Methylxone, Methylphenone, Methylam, Methylbuzine, Methylhonate, Methylfone, Methylphonate, Methylphonephone, Methylphosulmite, Methylphosulmite Wenchuzi, Milbemectin, Milbemycin oxime, Milneb, Mima 2 Nan, Mipahox, MIPC, Millex, MNAF, Mogchun, Methylate, Morosultap, Monfluorotrin, Monalide, Monislo Monoamitraz, monochloroacetic acid, monochromotophos, monolinurone, monomehipo, monosulfiram, monosulfuron, monosultap, monuron, monuron-TCA, morphanquat, moroxydin, morphothione, morzide, moxidectin, MPMC, MSMA, MTMC, musculla, microbutanyl, microzoline. , Myricyl alcohol, N- (ethylmercury) -p-toluenesulfonanilide, NAA, NAAm, nabam, naphthalofos, naredo, naphthalene, naphthaleneacetamide, naphthalic anhydride, naphthalophos, naphthoacetic acid, naphthylacetic acid, naphthylindane-1 , 3-Dione, naphthyloxyacetic acid, naproanilide, napropamide, napropamide-M, naptalam, natamicin, NBPOS, nebuurea, nebron, nendrin, neonicotin, nichlorphos, niclophen, nicrosamide, nicobiphen, nicosulfone, nicotine, nicotin sulfate, nifluridide Nikomycin, NIP, nipyracrophen, nipyrrophen, nitempirum, nithiazine, nitraline, nitrapyrin, nitrilacalve, nitrophen, nitrofluofen, nitrostyrene, nitrotar-isopropyl, nobormid, nonanol, norvomid, norea, norfrazone, nornicotin, norlon, novallon, nobiflumuron, nPA , Nuarimol, Nuranone, OCH, Octachlorodipropyl ether, Octinone, o-dichlorobenzene, Offrace, Ometoate, o-phenylphenol, Orbencarb, Orfuralua, Orthobencarb, Ortho-dichlorobenzene, Orthoflufamron, Orctalua, Orysastrobin, oryzarin, ostol, ostole, ostramone, obatron, obex, oxabetrinyl, oxadiardyl, oxadiazone, oxadixyl, oxamate, oxamil, oxapyrazon, oxapyrazone, oxapyrazone, oxapyrazone. , Oxadichromephon, oxine-copper, oxin-Cu, oxophosphate, oxpoconazole, oxycarboxyne, oxydemethone-methyl, oxydeprophos, oxydisulfoton, oxyenadenine, oxyfluorphen, oxymatrin, oxytetracycline, oxythioquino X, PAC, paclobutrazole, paicondin, paretrin, PAP, para-dichlorobenzene, parathurone, paracoat, parathion, palatin-methyl, parinol, paris green, PCNB, PCP, PCP-Na, p-dichlorobenzene, PDJ, Pebrate, Peginex, Pefrazoate, Pelargonic Acid, Penconazole, Pencyclon, Pendimethalin, Penphenate, Penflufen, Penfluron, Penoxalin, Penoxtam, Pentachlorophenol, Pentachlorophenyllaurate, Pentanochlor, Penthiopyrado, Pentomethrin, Pentoxazone, Parkroldecon, Perfluidon Permethrin, pesoxamide, PHC, phenamacryl, phenamacryl-ethyl, phenaminosulf, phenazineoxide, phenetacarb, phenisobum, fencapton, phenmedifam, fenmedifam-ethyl, phenobenzlone, phenothiol, phenothrin, fenproxide, fentoate, phenyl Mercury Urea, Phenylmercury Acetate, Phenylmercury Chloride, Phenylmercury Derivatives of Pyrocatechol, Phenylmercury Nitrate, Phenylmercury Salicylate, Holate, Hosacetim, Hosalon, Hosametin, Hosazetim, Hosazetin, Phoscyclotin, Phosdiphen, Josetil, Phosphorane, Phosphoran-Methyl, Hosglycine, Hosmet, Hosnicrol, Phosphamide, Phsphamiden, Hosphin, Phosphinotricin, Hoffhocarb, Phosphorus, Hostin, Hoxim, Hoxim-Methyl, Phenylide, Phenylphos, Phenylthrin, Picarbutrazox, Picardine, Picrolam, Picolinafene, Picoxystrobin , Pimalucin, Pindon, Pinoxaden, Piperlin, Piperazine, Piperonylbutoxide, Piperonylcyclonene, Piperophos, Pyrottanyl, Piprotanyl, Pipertal, Pyrimetaphos, Pyrimicalbu, Pyriminyl, Pyrimioxyphos, Pyrimiphos-ethyl, Pyrimiphos-methyl, Pival, Pivaldione PMA, PMP, polybutenes, polycarbamate, polychlorcampene, polyethoxyquinoline, polyoxin D, polyoxins, polyoxolim, polythialan, potassium phosphite, potassium azide, potassium cyanate, potassium ethylxanthogenate, potassium naphthenate, Potassium polysulfide, thiocyanic acid Potassium, pp'-DDT, psoralen, plecosen I, plecosen II, plecosen III, pretilachlor, pyrimidophos, pyrimisulfuron, probenazole, prochloraz, procronol, procyanosin, procimiden, prodiamine, profenophos, profluazole, proflularin, profluthrin , Propoxydim, Proflulite-Aminium, Proglinazine, Prohexadione, Prohydrojasmon, Promacyl, Promecarb, Promethon, Promethrin, Prometrine, Promlit, Pronamide, Propachlor, Propaphos, Propamide Propahos, Propaxahop, Propargit, Propatrin, Propazine, Propetanphos, Propazine, Propiconazole, Propazine, Propineb, Propisochlor, Propoxul, Propoxycarbazone, Propylisomer, Propyrrylfuron, Propizzamid, Proquinazide, Prothrel, Prosoralen , Prosulfocalb, prosulfuron, protidethione, prothiocarb, prothioconazole, prothiophos, protoate, protriphenbute, proxan, pyrimidophos, pyrinachlor, psoralen, psoralene, pidanone, pyrebamide, pyrethrin, pyracarbolid , Pyracronil, Pyracrostrobin, Pyraffulfen, Pyrafluprol, Pyramat, Pyrametstrone, Pyraoxystrobin, Pyrastrapol, Pyraziflumid, Pyrazolate, Pyrazolinate, Pyrazone, Pyrazophos, Pyrazosulfone, Pyrazothione, Pyrazoxifene, Pyrethrin, Pyrethrin I, Pyrethrin II, pyrethrins, pyribambenz-isopropyl, pyribambenz-propyl, pyribenecarb, pyribenzoxim, pyribuchicarb, pyricrol, pyridaben, pyridahole, pyridalyl, pyridaphenthion, pyridaphenthion, pyridaphenthion, pyridaphenthion, pyridaphenthione , Pyrimicarbe, pyrimidiphen, pyriminobac, pyriminostrobin, pyrimiphos-ethyl, pyrimiphos-methyl, Pyrimisulfan, Pyrimitate, Pyrinuron, Pyriophenone, Pyriprol, Pyrypropanol, Pyriproxyfen, Pyrisoxazole, Pyritiobac, Pyrroran, Pyrroxylone, Pyroxasulfone, Pyroxslam, Pyroxychlor, Pyroxyflu, Kinkaosuan, Kingkling, Quasia, Kinacetol, Kinalphos, Kinalphos-methyl, Kinazamide, Kinchlorac, Kinconazole, Kinmerak, Kinocramin, Kinomethionate, Kinonamide, Kinothione, Kinoxyphene, Kinthiophos, Kintozen, Kizarohop, Kizarohop-P, Quench, Quinging, Lavenzazole, Lahoxanide, R-Diniconazole , Rescarua, Resmethrin, Rodetanyl, Rodjaponin-III, Ribabylin, Lisulfuron, Lizazole, R-Metalaxil, Rodetanyl, Ronell, Rotenon, Lyania, Sabadilla, Safflephenacyl, Saijunmao, Saicentong, Salicylanilide, Sarifluophen -Bioaletrin, scladan, sicilyloside, sebutyrazine, sekbumethone, sedaxan, selamectin, semiamitraz, sesamex, sesamolin, sesson, setoxydim, sevin, shanagdia ankaolin, shuangzianan kaolin, S-hydroprene, sidurone, sifmichuvzi, sifumichuvzi , Silatran, silica erogel, silica gel, silthiofam, silthiopham, silthiophane, sylvex, simazine, simeconazole, simetone, simetrin, simeterin, simeteryne -Metoprene, S-methacrol, sodium arsenate, sodium azide, sodium chlorate, sodium cyanide, sodium fluoride, sodium fluoroacetate, sodium hexafluorosilicate, sodium naphthenate, sodium o-phenylphenoxide, sodium Orthophenylphenoxide, sodium pentachlorophenate, sodium pentachlorophenoxide, sodium polysulfide, sodium fluoride, sodium tetrathiocarbonate, sodium thiosocyanate, solan, sofamid, spiteram, spinosado, spi Logiclofen, spiromethifene, spirotetramato, spiroxamine, stylophos, streptomycin, strikinine, sulcatol, sulcofluone, sulcotrione, sulfarate, sulfentrazone, sulfiram, sulfuramide, sulfodazole, sulfomethurone, sulfosate, sulfosulfone, sulfotep , Sulfotepp, Sulfoxaflor, Sulfoxide, Sulfoxym, Sulfur, Sulfate, Sulfril Fluoride, Sulglycapine, Sulfosete, Sulfrophos, Sultropen, Swep, τ-Fulvalinate, Tabron, Tazimcarb, TBTO, TBZ, TCBA, TCBA, TCMTB, TCNB , TDE, tebuconazole, tebuphenozide, tebufenpyrado, tebuflokin, tebupyrinphos, tebutam, temtiurone, tecrophthalam, technazen, tecolum, tedion, teflubenzron, tefluthrin, tefryltrion, tembotrion, temefos, temefos Roxydim, teproloxidim, terraretrin, terbacil, terbucarb, terbuchlor, terbuhos, terbumeton, tergutyrazine, terbutor, terbutrin, terbutrine, terracrol, terramycin, terramicin, terramycin Temefos phos, tetraconazole, tetradiphon, tetradisul, tetraflulon, tetramethrin, tetramethylfluthrin, tetramine, tetranactin, tetraniliprol, tetrapion, tetrasul, thallium sulfate, thallium sulfate, temefos, , Θ-cypermethrin, thiabendazole, thiacloprid, thiadiazine, thiadifluol, thiamethoxam, thiamethurone, thiapronil, thiazaflulon, thiazflulon, thiazone, thiazopill, temefos, tycrophen, tidiadimin, thijiazuron, thiencarbazone, thifensulfuron Thiobencarb, thiocarboxym, thiochlorfenphim, thiochlorfenph Thiochlorphenzyme, thiocyanatodinitrobenzenes, thiram, thiodan, thiodiazol-copper, thiodicalve, thiophanocarb, thiofanox, thiofluoxymart, thiohenpa, thiomersal, thiomethone, thionazine, thiophanate, thiophanate-ethyl, thiophanate-methyl, thiophos , Thioquinox, thiosemicarbazide, thiosultap, thiotepa, tioxamil, tiram, thiuram, turingiencin, thiabendazole, thiazinyl, thiaphenacyl, thiaothian, TIBA, tifator, thiocarbadyl, thiochlorim, thioxazaphen, thioxymid, tyrpate, TMTD, torquelophos-methyl Torpralate, trifluanide, trillfluanide, tolylmercuric acetate, tomarin, topramison, toxaphen, TPN, tralcoxydim, tralocitrin, tralomethrin, traropyryl, transfluthrin, transpermethrin, tretamine, triacontanol, triazimephon, triazimenol, triafamon, Trialate, tri-alate, triamiphos, triampenol, trilatin, trialimol, triasulfuron, triazamate, triazbutyl, triaziram, triazophos, triazothione, triazoxide, tribasic copper chloride, acid-basic copper sulfate, tribenurone, tribuphos, Tributyltin oxide, tricamba, tricramide, triclopyr, trichlorfon, trichlormethaphos-3, trichloronat, trichloronate, trichlorotrinitrobenzene, trichlorfon, triclopil, triclopyricalbu, tricresol, tricyclazole, tricyclohexyl Tin hydroxide, tridemorph, tridiphan, trietazine, triphenmorph, triphenofos, trifloxystrobin, trifloxyflufuron, trifludimoxazine, triflumesopirim ,, triflumizole, triflumuron, triflularin, triflusulfuron, trihop, Trihopsime, triphorin, trihydroxytriazine, trimedrua, trimetacarb, trimethurone, trinexapac, triphenyltin, tryprene, tripropindane, triptolide, tritat Ku, trithiazole, trithiconazole, tritosulfone, trunk call, zoyerin, uniconazole, uniconazole-P, arborside, uredepa, valerate, varidamycin, varidamycin A, variphenalate, baron, bamidione, vanguard, vaniliprol, verno Rate, Vinclozoline, Vitamin D3, Warfarin, Xiaocheonryulin, Shinchuan, Shiwochunan, Shiwochunzi, XMC, Xylacrol, Xylenols, Xylylcarb, Ximiazole, Ishidin, Zalylamide, Zeatin, Zenciaoan, Zinc phosphide, ζ- Cipermethrin, zinc naphthenate, zinc phosphide, thiazole zinc, thiazole zinc, trichlorophenolate zinc, trichlorophenoxide zinc, geneb, dilam, zolaprophos, zukmarin, zoxamide, zoanchunzi, zocaoan, zochunzi, zuomifuanglong, α-Chlorohydrin, α-Exdison, α-Multistriatin, α-naphthylacetic acids, and β-Exdison,
(2) Molecules shown below

In the present specification, this molecule is named "AI-1" for the purpose of ease of use.
(3) A molecule known as Lotilaner having the following structure

And (4) Structure-active ingredients of the following molecular tables AM listed in Table A

As used in the present disclosure, each of the above is an active ingredient, and two or more are active ingredients. For more information, see "Compendium of Pesticide Common Names" (described in Alanwood.net and other editions), including the online version of "The Pesticide Manual" (described in bcpcdata.com).

The term "alkenyl" means an acyclic, unsaturated (at least one carbon-carbon double bond), branched or unbranched substituent consisting of carbon and hydrogen, eg, There are vinyl, allyl, butenyl, pentenyl, and hexenyl.

The term "alkenyloxy" further means an alkenyl consisting of a carbon-oxygen single bond, including, for example, allyloxy, butenyloxy, pentenyloxy, hexenyloxy.

The term "alkoxy" further means an alkyl consisting of a carbon-oxygen single bond, including, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and tert-butoxy.

The term "alkyl" means an acyclic, saturated, branched or non-branched substituent consisting of carbon and hydrogen, eg, methyl, ethyl, propyl, isopropyl, butyl, and tert-butyl. There is.

The term "alkynyl" means an acyclic, unsaturated (at least one carbon-carbon triple bond), branched or unbranched substituent consisting of carbon and hydrogen, eg, ethynyl. , Propargyl, butynyl, and pentynyl.

The term "alkynyloxy" further means alkynyl consisting of a carbon-oxygen single bond, including, for example, pentynyloxy, hexynyloxy, heptynyloxy, and octynyloxy.

The term "aryl" means a cyclic, aromatic substituent consisting of hydrogen and carbon, such as phenyl, naphthyl, and biphenyl.

The term "biopesticide" means a biological pest control agent for microorganisms, commonly applied in a manner similar to chemical pesticides. They are usually bacterial, but there are also examples of fungal control agents including the genus Trichoderma spp. And Ampelomyces quisqualis. An example of a known biopesticide is Bacillus thuringiensis, a bacterial disease of the order Lepidoptera, Coleoptera and Diptera. Biopesticides include products based on:
(1) Insect pathogenic filamentous fungi (eg, Metarhizium anisoplier),
(2) Insect pathogenic nematodes (eg, Steinernema fertiae), and (3) Insect pathogenic viruses (eg, Cydia pomonella granulovirus).

Other examples of insect pathogenic organisms include, but are not limited to, baculovirus, protozoa, and Microsporidia. For the avoidance of doubt, biopesticides are considered active ingredients.

The term "cycloalkenyl" means a monocyclic or polycyclic, unsaturated (at least one carbon-carbon double bond) substituent consisting of carbon and hydrogen, eg, cyclobutenyl, cyclopentenyl. , Cyclohexenyl, norbornenyl, bicyclo [2.2.2] octenyl, tetrahydronaphthyl, hexahydronaphthyl, and octahydronaphthyl.

The term "cycloalkenyloxy" further means cycloalkenyl consisting of a carbon-oxygen single bond, eg, cyclobutenyloxy, cyclopentenyloxy, norbornenyloxy, and bicyclo [2.2.2] oct. There is tenyloxy.

The term "cycloalkyl" means a monocyclic or polycyclic, saturated substituent consisting of carbon and hydrogen, eg cyclopropyl, cyclobutyl, cyclopentyl, norbornyl, bicyclo [2.2.2] octyl, And decahydronaphthyl.

The term "cycloalkoxy" further means cycloalkyl consisting of a carbon-oxygen single bond, such as cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, norbornyloxy, and bicyclo [2.2.2] octyl. There is oxy.

The term "halo" means fluoro, chloro, bromo, and iodine.

The term "haloalkoxy" further means an alkoxy consisting of one to the maximum possible number of the same or different halos, eg fluoromethoxy, trifluoromethoxy, 2,2-difluoropropoxy, chloromethoxy, trichloromethoxy. , 1,1,2,2-tetrafluoroethoxy, and pentafluoroethoxy.

The term "haloalkyl" further means alkyl consisting of the same or different halos from one to the maximum possible number, eg fluoromethyl, trifluoromethyl, 2,2-difluoropropyl, chloromethyl, trichloromethyl, And 1,1,2,2-tetrafluoroethyl.

The term "heterocyclyl" means aromatic, cyclic substituents that can be fully saturated or partially unsaturated or completely unsaturated, where the cyclic structure is at least one carbon and at least one. It contains 10 heteroatoms, the heteroatom being nitrogen, sulfur, or oxygen. The following are examples.

が含まれる。 (1) Examples of aromatic heterocyclyl substituents include, but are not limited to, benzofuranyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, benzothienyl, benzothiazolyl cinnolinyl, flanyl, indazolyl, indolyl, imidazolyl, isoindyl, isoquinolinyl, Isothiazolyl, isooxazolyl, oxadiazolyl, oxazolinyl, oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl, pyrazolyl, pyridadinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl, tetrazolyl, thiazolinyl, thiazolyl, thiazolyl, triazolyl, and triazolyl.
(2) Examples of fully saturated heterocyclyl substituents include, but are not limited to, piperazinyl, piperidinyl, morpholinyl, pyrrolidinyl, tetrahydrofuranyl, and tetrahydropyranyl;
(3) Examples of partially or completely unsaturated heterocyclyl substituents include, but are not limited to, 1,2,3,4-tetrahydro-quinolinyl, 4,5-dihydro-oxazolyl, 4,5-dihydro-1H. −Pyrazolyl, 4,5-dihydro-isooxazolyl, and 2,3-dihydro- [1,3,4] -oxadiazolyl; and (4) additional examples of heterocyclyls include:

Is included.

The term "area" means a habitat, breeding ground, plant, seed, soil, substance, or environment in which pests can grow, grow, or pass by. For example, areas are areas where crops, trees, fruits, grains, feeds, vines, lawns, and / or ornamental plants grow, areas where livestock live, and internal or external surfaces of buildings (where grains are stored). Etc.), construction materials used in the building (such as impregnated wood), and the soil around the building.

The phrase "MoA substance" is used in irac-online. org. IRAC MoA classification v. Means a substance having the mechanism of action (“MoA”) shown in 7.3, the following is shown:
(1) Acetylcholinesterase (AChE) inhibitor,
(2) GABAergic chloride channel antagonist,
(3) Sodium channel modulator,
(4) Nicotinic acetylcholine receptor (nAChR) agonist,
(5) Nicotinic acetylcholine receptor (nAChR) allosteric activator,
(6) Chloride channel activator,
(7) Juvenile hormone imitation,
(8) Various non-specific (multisite) inhibitors,
(9) Modulator of the string organ,
(10) Tick growth inhibitor,
(11) Insect midgut membrane microbial disturber,
(12) Mitochondrial ATP synthase inhibitor,
(13) Decoupling agent for oxidative phosphorylation through disturbance of proton gradient,
(14) Nicotinic acetylcholine receptor (nAChR) channel blocker,
(15) Chitin biosynthesis inhibitor, type 0,
(16) Chitin biosynthesis inhibitor, type 1,
(17) Diptera molting disturber,
(18) Ecdysone receptor agonist,
(19) Octopamine receptor agonist,
(20) Mitochondrial complex III electron transfer inhibitor,
(21) Mitochondrial complex I electron transfer inhibitor,
(22) Voltage-gated sodium channel blocker,
(23) Acetyl-CoA carboxylase inhibitor,
(24) Mitochondrial complex IV electron transfer inhibitor,
(25) Mitochondrial complex II electron transfer inhibitor, and (28) Ryanodine receptor modulator.

The phrase "MoA substance group alpha" (hereinafter "MoAMGA") collectively means the following substances. Abamectin, acephate, acequinosyl, acetamipride, acrinathrin, aranicalve, aldicarb, allethrin, α-cypermethrin, aluminum phosphate, amitraz, azamethifos, azinephos-ethyl, azinephos-methyl, azocyclotin, benziocarb, benfracarb, benzulfruthrin, β- -Cypermethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenylisomer, bioallethrin, bistriflulon, bolux, buprofezin, buttocarboxym, butoxycarboxym, kazusaphos, calcium phosphate, carbalyl, carbofuran, carbosulfane, cartap hydrochloride, Chlorpyrifos, chlordan, chlorethoxyphos, chlorphenapir, chlorphenbinphos, chlorfluathrin, chlormephos, chloropicrin, chloropyrifos, chlorpyrifos-methyl, chromafenozide, clofenthedin, clothianidin, kumaphos, cyanide, cyanophos, Cyantraniliprol, cycloprothrin, cyenopyraphen, cyfluthrin, cypermethrin, cypermethrin, cypermethrin, cypermethrin, cypermethrin, cilomadin, d-cis-trans-allethrin, DDT, deltamethrin, demethon-S-methyl, diaphenthiron, Diazinone, dichlorvos / DDVP, dichlorpyrifos, difluorovidazine, diflubenzlone, dimethate, dimethylbinphos, dinotefuran, disulphoton, DNOC, d-trans-allethrin, emamectin benzoate, empentrin, endosulfane, EPN, esphenvalerate, ethiophencarb , Etofenprox, etoxazole, famfur, phenamiphos, phenazakin, fenbutatin oxide, fenitrothione, phenocarb, phenoxycarb, phenpropathrin, phenpyroxymate, fenthion, fenvalerate, fronicamid, fluacripirim, flubenzidamide, flucycloxlone, flucitrinate Phenoxron, flumethrin, flupyraziflon, formanate, hostizet, fratiocarb, γ-cypermethrin, halphenprox, halophenozide, heptenophos, hexaflumron, hexithiazox, hydramethylnone, hydroprene, imi Ciaphos, imidacloprid, imiprosulin, indoxacarb, isofenphos, isoprocalve, isoxathione, cadesulin, quinoprene, λ-cypermethrin, repimethrin, lurenuron, malathion, mecarbam, metaflumison, metamidphos, methiadation, methiocarb, methaminol ) Salicylate, methoxychlor, methoxyphenozide, methyl bromide, metorcarbe, mevinphos, milbemectin, monochromotophos, naredo, nicotine, nitempirum, novallon, nobiflumron, oxamil, oxydemethrin-methyl, palatine, palatine-methyl, permethrin, phenothrin, fentoate , Hosalon, Hosmet, Phosphamiden, Hosphin, Hoxime, Pyrimicarb, Pyrimiphos-methyl, Paralesulin, Profenophos, Propargit, Propetanphos, Propoxul, Prothiophos, Pymetrodin, Pyraclophos, Pyretrin, Pyridaben, Pyridafenthion, Pyrimidiphen , Silafluofen, spinnetram, spinosad, spirodiclofen, spiromesifen, spirotetramato, sulfurlamide, sulfotep, fluhoxaflor, sulfuryl fluoride, talisman, τ-fluvalinate, tebuphenozide, tebufenpyrado, tebupyrinphos, tefluthrin Temefos, terbuphos, tetrachlorobinphos, tetrediphon, tetramethrin, tetramethrin, θ-cypermethrin, thiacloprid, thiamethoxam, thiocyclam, thiodicalve, thiophanox, thiomethon, thiosultap-sodium, tolfenpyrad, tralomethrin, transfluthrin, triazamate, triazophos Triflumron, trimetacarb, bamidthione, XMC, xylylcarb, ζ-cypermethrin, and zinc phosphate. To avoid doubt, each of the above substances is an active ingredient.

The term "pest" means an organism that is harmful to humans or human concerns (crop, food, livestock, etc.), which is an arthropod, aphid, or termite. From the phylum, specific examples are ants, aphids, beetles, stains, cockroaches, crickets, scissors, flea, flies, grasshoppers, horizontal bait, termites (including fungus), locusts, mites, moths, nematodes, scale insects, komukade. , Termites, horse mackerel, ticks, scale insects, and scale insects, with additional examples of the following pests.

(1) Chelicerata, Myriapoda, Crustacean, and Hexapoda,
(2) Arachnids, maxillopoda, connecting nets, and insects,
(3) Lice eyes. A non-exhaustive list of specific genera is not limited to, but is limited to Haematopinus spp., Hoplopleura spp., Linognatus spp. ), And Polyplax spp. Non-exhaustive list of specific species, but not limited to, Haematopinus asini, Haematopinus suis, Linognatus setos, Linognathus setos, Linognathus setos, Includes Pediculus humanus capitis, Pediculus humanus humanus, and Pthirus pubis.

(4) Coleoptera. The non-exhaustive list of specific genera is not limited to, but is not limited to the genus Acanthoselides spp., The genus Agriotes spp., The genus Anthonomus spp. ), Apogonia spp., Auracophora spp., Bruchus spp., Cerosterna spp., Serotoma shoot sp. Genus species (Ceutorhinchus spp.), Caetocnema spp., Collaspis spp., Ctenicera spp., Curculio spp. ), Diablotica spp., Hypera spp., Ips spp., Lyctus spp., Megacelis spp., Meligetes spp. Species (Meligethes spp.), Othiolincus sp. (Otiorhinchus spp.), Pantomorus spp. ), Linkites spp., Rynchophorus spp., Scolytus spp., Sphenophorus spp., Sphophorus spp., Sitophilus spp. Includes and includes, but is not limited to, a non-exhaustive list of specific species of the genus Tribolium spp. gla bripennis), Antonomusu grandis (Anthonomus grandis), Ateniusu-Supurechurusu (Ataenius spretulus), Atomaria-Rinearisu (Atomaria linearis), Bochinoderesu-Pung Cu Chi vent squirrel (Bothynoderes punctiventris), Burukusu-Pisoramu (Bruchus pisorum), Karosoburukusu-Makuratsusu (Callosobruchus maculatus, Carpofilus hemipterus, Cassida vittata, Serotoma triflucata, Conoderus asparagus beetle, Conoderus asparagus beetle scalaris, Conoderus stigmosus, Conoderus nenufar, Aofukikogane (Cotinis nitida), Clioceris sparagi (Crioceris sparagi) pusillus, Cryptolestes turcisus, Cylindrocopturus adspersus, Deporaus marginatus, Deporaus marginatus Epilachna varivestis, Faustinus cubae, Hylobius pales, Hypera postica, Hipera poster, Hipotemes ham Rashioderuma-Serikorune (Lasioderma serricorne), Leptinotarsa Desemurineata (Leptinotarsa decemlineata), Riogenisu-Fusukusu (Liogenys fuscus), Riogenisu-Sutsurarisu (Liogenys suturalis), Risoroputorusu-Orizofirusu (Lissorhoptrus oryzophilus), Maekorasupisu-Joribechi (Maecolaspis joliveti), Meranotsusu - Communis (Melanoutus communis), Meligethes aeneus, Meloronta melolonza, Oberea brevis, Oberea brevis, Oberea linearis Mercator (Oryzaephilus mercator), Oryza Efiru vinegar Surinamenshisu (Oryzaephilus surinamensis), Ourema-Meranopusu (Oulema melanopus), Ourema oryzae (Oulema oryzae), Firofaga-Kuyabana (Phyllophaga cuyabana), Popiria-japonica (Popillia japonica), professional Sutefanusu · Tsurunkatsusu (Prostephanus truncatus), Rizoperuta-Dominican (Rhyzopertha dominica), Shitona-Rineatsusu (Sitona lineatus), Shitofirusu-Guranariusu (Sitophilus granarius), Shitofirusu oryzae (Sitophilus oryzae), Shitofirusu-Zeamaisu (Sitophilus zeamais), Sutegobiumu-Paniseumu (Stegobium paniceum), Tribium castaneum, Tribium sitophilus, Trogoderma variabile, and Zables tenevile. es) is included.

(5) Leather wings. A non-exhaustive list of specific species includes, but is not limited to, Forficula auricularia.

(6) Cockroach eyes. The non-exhaustive list of specific species is not limited to, but is not limited to, Blattella germanica, Blatta orientalis, Parco blatta pensylvanica, Periplaneta Americana. ), Periplaneta australasiae, Periplaneta brunnea, Periplaneta fuliginosa, Periplaneta fuliginosa, Periplaneta fuliginosa, Pycnoserus sulis

(7) Diptera. A non-exhaustive list of specific genera is not limited to, but is limited to Aedes spp., Agromiza spp., Anastrepha spp., Anofeles spp. ), Bactrocera spp., Ceratis spp., Chrysops spp., Cochliomya spp., Contalina sp. Culex spp.), Dacineura spp., Delia spp., Drosophila spp., Fannia spp., Hylemia spp. Examples include Liriomyza spp., Musca spp., Holbia spp., Tabanus spp., And Tipula spp. A non-exhaustive list of specific species is not limited to, but is limited to, Anastrepha frontella, Anastrepha suspenza, Anastrepha ludens, Anastrepha ludens, Anastrepha oblica stra brica. Kukurubitae (Bactrocera cucurbitae), Bakutorosera-Dosarisu (Bactrocera dorsalis), Bakutorosera-Inbadensu (Bactrocera invadens), Bakutorosera-Zonata (Bactrocera zonata), Serachichisu-Kapitata (Ceratitis capitata), Dashineura-Brassica (Dasineura brassicae), Delia Puratsura ( Delia plata, Fania canicularis, Fannia scalaris, Gasterofilus intestinalis, Glasilia perseiae glaciae glacia Hypoderma lineatum, Liriomyza brassicae, Melophagus ovinus, Musca autumnalis, Musca autumnalis, Musca autumnalis, Musca domus (Oscinella frit), Pegomya betae, Psila rosae, Lagoletis cerasi, Lagoletis pomonella (Rhagoletis pomonella) (Sitodophilosis mosella), and Stomoxys calcitra ns) is included.

(8) Hemiptera. A non-exhaustive list of specific genera is not limited to, but is limited to, Adelges spp., Aulacas spp., Aphlophora spp., Aphis spp. ), Bemisia spp., Celoplastes spp., Chionaspis spp., Chrysomphalus spp., Chrysomphalus spp., Coccus sp. Genus genus (Emposas spp.), Lepidosafes genus (Lepidosafes spp.), Laginotomus spp., Ligus spp., Macrosifmus spp. ), Nezara spp., Philaenus spp., Phytocoris spp., Piezodolus spp., Planocox spp. Cox sp. Specs include spp.), Trialeurodes spp., Triatoma spp., And Unaspis spp. A non-exhaustive list of certain species includes Acrosternum hirare, Acyrthosiphon pisum, Aleyrodes proletella, Aleurodix dispersus (Aleurodes proletella) , Aleurotrixus floccosus, Aphisca bigutula biguttura, Aoniziella aurantii, Aonidiella aurantii, Aphis gosipiis ), Aurakorutsumu solani (Aulacorthum solani), Bemisia Arugenchihorii (Bemisia argentifolii), Bemisia Tabashi (Bemisia tabaci), Brisas Reukoputerusu (Blissus leucopterus), Burakikorinera-aspartic (Brachycorynella asparagi), Bureven'nia Lech (Brevennia rehi), Burebikorine-Burashikae (Brevicoryne brassicae), Karokorisu-Noruvegikusu (Calocoris norvegicus), Seropurasutesu-Rubensu (Ceroplastes rubens), Shimekusu-Hemiputerusu (Cimex hemipterus), Shimekusu-Rekutsurariusu (Cimex lectularius), Daguberutsusu-Fashiatsusu (Dagbertus fasciatus), Jikeropusu - Furukatsusu (Dichelops furcatus), Jiurafisu Nokia (Diuraphis noxia), Jiahorina-citri (Diaphorina citri), Jisafisu planta Guinea (Dysaphis plantaginea), Dysdercus Sutsurerusu (Dysdercus suturellus), Edessa, Mejitabunda (Edessa meditabunda), Eriosoma-Ranigerumu (Eriosoma langer um), Eurigaster Maura, Eucystus heros, Eustictus servus, Heropertis anthirici herocipertis heroci te viraci heroci siphum erocite , Idioscopus nitidulus, Laodelfax striatelrus, Leptocorisa oratorius, Leptocorisa oratorius, Leptocorisa varicornis Maconellicoccus hirsutus), Makuroshifumu-Oihorubiae (Macrosiphum euphorbiae), Makuroshifumu-Guranariumu (Macrosiphum granarium), Makuroshifumu-Rosae (Macrosiphum rosae), macro terrestris-click Adori Linea Tsusu (Macrosteles quadrilineatus), Mahanaruba-Furinbiorata (Mahanarva frimbiolata), Metoporofiumu-Jirozumu (Metopolophium dirhodum), Mikuchisu-Rongikorunisu (Mictis longicornis), Myzus persicae (Myzus persicae), Nehotetchikisu-Shinkuchipesu (Nephotettix cinctipes), Noirokosupusu Longhi lost squirrel (Neurocolpus longirostris), Nezara-Birizura (Nezara viridula), Niraparubata-Rugensu (Nilaparavata lugens), Parlatria pergandii, Parlatria ziziffi, Peregrinus maidis, Phylloxera phiholia, macrosiphum Rumesu-Piseae (Physokermes piceae), Fitokorisu-Karihorunikusu (Phytocoris californicus), Fitokorisu-Rerachibusu (Phytocoris relativus), Piezodorusu-Guirudinyi (Piezodorus guildinii), Poeshirokapususu-Rineatsusu (Poecilocapsus lineatus), Pusarusu-Basshinikora (Psallus vaccinicola), Shudashisuta - Peruseae (Pseudacysta perseae), shoe de Cox Burebipesesu (Pseudococcus brevipes), Quadra spin Geo Tsusu-Perunishiosusu (Quadraspidiotus perniciosus), Roparoshifamu-Maidisu (Rhopalosiphum maidis), Roparoshifamu Padi (Rhopalosiphum padi), Saissechia-Oreae (Saissetia oleae), Sukaputokorisu - Castanea (Scaptocoris castanea), Shizafisu-Guraminumu (Schizaphis graminum), Shitobion-Abenae (Sitobion avenae), Sogatera-Furushifera (Sogatella furcifera), Toriareurodesu-Baporariorumu (Trialeurodes vaporariorum), Toriareurodesu-Abuchironeusu (Trialeurodes abutiloneus), Unasupisu - Examples include, but are not limited to, Unaspis yanonensis and Zulia entleriana.

(9) Hymenoptera. A non-exhaustive list of specific genera includes Acromyrmex spp., Atta spp., Camponotus spp., Diprion spp., Holmica. Genus species (Formica spp.), Monomorium spp., Neodiprion spp., Pogonomyrmex spp., Polystes sp. Spp.), The genus Vespula spp., And the genus Xylocopa spp. Are, but are not limited to. A non-exhaustive list of certain species includes Atalia rosae, Atta texana, Iridomyrmex humilis, Monomorium mori, Monomorium, Monomorium, Monomorium, and Monomorium. , Solenopsis invicta, Solenopsis geminata, Solenopsis molesta, Solenopsis selipsis rypsis, Solenopsis lictery, Solenopsis lictery Includes, but is not limited to.

(10) Termites. A non-exhaustive list of specific genera is not limited to, but is not limited to, Copttermes spp., Cornittermes spp., Cryptotermes spp. Spp.), Carotermes spp., Incisitermes spp., Macrotermes spp., Marginitermes spp., Microcellomes spp., Microcellomes spp. Spp.), Procornitermes spp., Reticulitermes spp., Schedorhinotermes spp., And Zootermopsis spp. A non-exhaustive list of specific species includes Copttermes curvinathus, Copttermes frenchi, Copttermes formosanus, Heterotermes uremus, Heterotermes aureus. Microtermes obesi, Reticulitermes banyulensis, Reticulitermes glassei, Reticulitermes flavitemes Hesperimes flavites, Reticulitermes flavipes Reticulitermes hesperus, Reticulitermes santonensis, Reticulitermes speratsus, Reticulitermes speratus, Reticulitermes speratus, Reticulitermes serisites, Reticulitermes speratus Not limited.

(11) Lepidoptera. A non-exhaustive list of specific genera includes Adoxophyes spp., Agrotis spp., Argyrotaenia spp., Cacoecia spp., Cacoecia spp. (Caloptilia spp.), Kilo spp., Chrysodeixis spp., Collias spp., Crambus spp., Diaphania sp. , Diatraea spp., Airias spp., Ephestia spp., Epimesis spp., Feltia spp., Fertia spp. Gortina spp.), Helicovelpa spp., Heliothis spp., Indalbella spp., Lithocolletis spp. Lithocolletis spp. Las losoma spp. Genus species (Malacosoma spp.), Peridroma spp., Phyllonoricter spp., Pseudaletia spp. , Synanthedon spp., And Yponomeuta spp., But are not limited thereto. A non-exhaustive list of certain species includes Achaea janata, Adoxophyes orana, Agrotis ipsilon, Alabama algama aracia (Alabama algala). , Amyueroisu-Toranshiterra (Amyelois transitella), Ana Camptosar Death Defekutaria (Anacamptodes defectaria), Anarushia-Rineatera (Anarsia lineatella), Anomisu-Saburifera (Anomis sabulifera), anti-calcia-Genmatarisu (Anticarsia gemmatalis), Arukipusu-Arugirosupira (Archips argyrospila ), Archips rosana, Argyrotaenia citrana, Autographa gamma, Bonagota cranaodes (Bonagota cranacrabora), Bonagota cranacrabora crana thurberiella), coupler Rechikurana (Capua reticulana), Karuposhina-Nipomenshisu (Carposina niponensis), Kurumechia transformer Versa (Chlumetia transversa), Korisutonoira-Rosaseana (Choristoneura rosaceana), Kuna file potter's wheel Chis-Mejinarisu (Cnaphalocrocis medinalis), Konopomorufa-Kuramerera (Conopomorpha kramerella), Cossus cossus, Cydia cariana, Cydia funebrana, Cydia funebrana, Cydia pea pea moth, Cydia pea moth, Cydia pea pea moth pomonella), Darna diducta, diatlae Diatraea saccharalis, Diatraea grandiosella, Airias insulana, Airias vittella, Ecgitrofa auranchi , Efestia cautella, Efestia elutella, Efestia kuehniella, Epinotia apolema epinotia aporema , Yupoeshiria-Anbiguera (Eupoecilia ambiguella), Oikisoa Au xylylene Alice (Euxoa auxiliaris), Gurahorita-Moresuta (Grapholita molesta), Hejirueputa-Injikata (Hedylepta indicata), Helicoverpa-Arumigera (Helicoverpa armigera), Helicoverpa zea (Helicoverpa zea) , Heliothis virescens (Heliothis virescens), Herura-Undarisu (Hellula undalis), Kei Feria Rikoperushisera (Keiferia lycopersicella), Roishinodesu-Orubonarisu (Leucinodes orbonalis), Roikoputera-Kofeera (Leucoptera coffeella), Roikoputera-Marihoriera (Leucoptera malifoliella), Lobesia botrana, Loxagrotis albicosta, Lymantria dispar, Lyonetia clerkera, Lyonetia clerkera Rashikae (Mamestra brassicae), Marca-Tesutsurarisu (Maruca testulalis), Mechisa Plana (Metisa plana), Michimuna-Unikunputa (Mythimna unipuncta), Neoroishinodesu-Eregantarisu (Neoleucinodes elegantalis), Ninfura-Depunkutarisu (Nymphula depunctalis), Operofutera-Burumata (Operophtera brumata), Osutorinia-Nubirarisu (Ostrinia nubilalis), Okishijia-Besuria (Oxydia vesulia), Pandemisu-Serasana (Pandemis cerasana), Pandemisu-Heparana (Pandemis heparana), Papillio-Demodokusu (Papilio demodocus), Pekuchinohora-Goshipiera (Pectinophora gossypiella), Peridoroma-Saushia (Peridroma saucia), Periroikoputera-Kofeera (Perileucoptera coffeella), Futorimaea-Operukurera (Phthorimaea operculella), Firokunisuchisu-Shitorera (Phyllocnistis citrella), Pierisu rapa (Pieris rapae), Purachipena-Sukabura (Plathypena scabra) , Prodia interpunktera, Plutera xylostella, Polychromis vita, Price endocalpa (Prays endocarpa), Price endocalpa, Price endera ), Pseudoplusia includens, Rachiplusia nu, Skillpophaga incerturas, Sesamia inferens, Sesamia inferensa nagrioides), settler-Nitensu (Setora nitens), Shitotoroga-Serearera (Sitotroga cerealella), Suparuganochisu-Pireriana (Sparganothis pilleriana), Spodoptera exigua (Spodoptera exigua), Spodoptera Furugiperuta (Spodoptera frugiperda), Spodoptera Eridania (Spodoptera eridania) , Tecla basilides, Tineola bisselliella, Trichoplusia ni, Tuta absoluta, Zota absoluta, Zoezera cofair Includes, but is not limited to.

(12) Paraphyletic chewing eyes. A non-exhaustive list of specific genera is not limited to, but is limited to Anaticola spp., Bovicola spp., Cheropistes spp., Goniodes spp. ), The genus Menacanthus spp., And the genus Trichodectes spp. The non-exhaustive list of specific species is not limited to, but is not limited to, Bovicola bovis, Bovicola caprae, Bovicola ovis, Keropistes meleagridis, Chelopis. Disimiris (Goniodes dissimilis), Goniodes gigas, Menacanthus stramineus, Menopon gallinae (Menopon gallinae), and Tricodes cites (not limited to Menopon gallinae), and tricodes.

(13) Orthoptera. A non-exhaustive list of specific genera includes, but is not limited to, Spur-throated grass species (Melanoplus spp.) And Pterophylla spp. The non-exhaustive list of specific species is not limited to, but is limited to Anables simplex, Glylotalpa africana, Glylotalpa australis, Glylotalpa australis, Glylotalpa australalis, Glylotalpa australis, Glylotalpa australis Hexadactilla (Glyllotalpa hexadactyla), Locusta migratorya, Microcentrum retinerve, Sistocerca gregalia (Schistocerca cateca)

(14) Flea eyes. A non-exhaustive list of specific species is not limited to, but is not limited to, Ceratopyllus gallinae, Ceratopyllus niger, Ctenocephalides canis, Ctenocephalides canis. Includes Centocephalides fleas), and Pulex irritans.

(15) Argulus eyes. The non-exhaustive list of certain species includes Lepeophtheirus salmonis, Lepeophtheirus lectoralis, Caligus Elongatus, and Caligus Elongatus, and Caligus. Not done.

(16) Thrips. A non-exhaustive list of specific genera is not limited to, but is not limited to, Cariotrips spp., Frankliniella spp., Skilltotrips spp., And Trips spp. Species (Trips spp.) Are included. A non-exhaustive list of specific species includes Frankliniella fusca, Frankliniella occidentalis, Frankliniella schultiyli, frankliniella thripsyliella, frankliniella thripsii ), Heriotoripusu-Haemoroidarisu (Heliothrips haemorrhoidalis), Ripihorotoripusu-Kuruentatsusu (Rhipiphorothrips cruentatus), skills Totori TOPS, Kitri (Scirtothrips citri), skills Totori TOPS-Dosarisu (Scirtothrips dorsalis), and tennis male Lips Roparantenarisu (Taeniothrips rhopalantennalis), Thrips - Examples include, but are not limited to, Trips hawaiiensis, Thrips nitropillosus, Trips orientalis, and Trips tabaci.

(17) Thysanura. A non-exhaustive list of specific genera includes, but is not limited to, Lepisma spp. And Thermobia spp.

(18) Tick eyes. A non-exhaustive list of specific genera, but not limited to, Acarus spp., Acculops spp., Boophilus spp., Demodex spp. ), Dermacentor spp., Epitrimerus spp., Eriophies spp., Ixodes spp., Oligonychus spp., Oligonychus spp. Genus species (Panonychus spp.), Rhizoglyphos spp., And Tetranychus spp. Are included. A non-exhaustive list of certain species includes Acarapis woodi, Acarus siro, Aceria mangiferae, Acrops licopelis paces licoper , Aculus schlechtendali, Ambrioma americanum, Brevipalpus obovatus, Brevipalpus hoevilp Pteroniscinus (Dermatophagoides pteronysinus), Eotetranychus carpini, Notoedress cati, Oligonychus cous ulmi (Panonychus ulmi), Firokoputoruta-Oreibora (Phyllocoptruta oleivora), poly file Gota Luso Nemusu-Ratsusu (Polyphagotarsonemus latus), Rhipicephalus-sanguineus (Rhipicephalus sanguineus), Sarukoputesu-Sukabiei (Sarcoptes scabiei), Tegorofusu-Peruseafurorae (Tegolophus perseaflorae), tetra Includes, but is not limited to, Nyx ulticae, and Varroa desertor.

(19) Symphyla eyes. A non-exhaustive list of specific species includes, but is not limited to, Scuitgerella immaculata.

(20) Nematode phylum. A non-exhaustive list of specific genera is not limited to, but is not limited to Aferenchoides spp., Belonolaimus spp., Criconemela spp., Ditylenchus sp. Spp.), Heterodera spp., Hirschmanniella spp., Hoploraimus spp., Meloidogyne spp. , And the genus Radofolus spp. A non-exhaustive list of certain species includes Dirofilaria imitis, Heterodera zeae, Meloidogyne incognita, Meloidogyne incognita, Meloidgine cavani cavani cavani ), Radopholus similis, and Rotylenchurus reniformis, but not limited to these.

The phrase "effective amount of pesticide" exerts an observable effect on pests (eg, the effect of necrosis, death, suppression, prevention, removal, destruction, or reduction of pest outbreak and / or activity in an area). Means the amount of pesticides needed for. This effect occurs when a pest population is repelled from an area, when the pest is incapacitated in or around the area, and / or when the pest is eradicated in or around the area. Is. Of course, a combination of these effects can also occur. Generally, the pest population, activity, or both are preferably reduced by more than 50 percent, preferably by more than 90 percent, and most preferably by more than 99 percent. In general, the effective amount of pesticides for agricultural purposes is from about 0.0001 grams per hectare to about 5000 grams per hectare, preferably from about 0.0001 grams per hectare to about 500 grams per hectare. Even more preferably, it is about 0.0001 grams per hectare to about 50 grams per hectare.

式中：
（Ａ） Ｒ^１、Ｒ^５、Ｒ^６、Ｒ^１１、およびＲ^１２は各々独立してＨ、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、（Ｃ_１−Ｃ_４）アルキル、（Ｃ_１−Ｃ_４）ハロアルキル、（Ｃ_１−Ｃ_４）アルコキシ、および（Ｃ_１−Ｃ_４）ハロアルコキシからなる群から選択される；
（Ｂ） Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立してＨ、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、（Ｃ_１〜Ｃ_４）アルキル、（Ｃ_２〜Ｃ_４）アルケニル、（Ｃ_２〜Ｃ_４）アルキニル、（Ｃ_１〜Ｃ_４）ハロアルキル、（Ｃ_１〜Ｃ_４）アルコキシおよび（Ｃ_１〜Ｃ_４）ハロアルコキシからなる群から選択される；
（Ｃ） Ｒ^７は、（Ｃ_１−Ｃ_６）ハロアルキルである；
（Ｄ） Ｒ^９は、（Ｆ）、Ｈ、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、（Ｃ_１−Ｃ_４）アルキル、（Ｃ_１−Ｃ_４）ハロアルキル、（Ｃ_１−Ｃ_４）アルコキシ、および（Ｃ_１−Ｃ_４）ハロアルコキシからなる群から選択される；
（Ｅ） Ｒ^１０は、（Ｆ）、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、（Ｃ_１〜Ｃ_４）アルキル、（Ｃ_２〜Ｃ_４）アルケニル、（Ｃ_２〜Ｃ_４）アルキニル、（Ｃ_１〜Ｃ_４）ハロアルキル、（Ｃ_１〜Ｃ_４）アルコキシ、及び（Ｃ_１〜Ｃ_４）ハロアルコキシからなる群から選択され、
（Ｆ） Ｒ^９及びＲ^１０は共に、３員〜５員の飽和または不飽和のヒドロカルビル環を任意で形成することができ、
当該ヒドロカルビル環は、Ｆ、Ｃｌ、Ｂｒ、Ｉ、及びＣＮからなる群から独立して選択される１つ以上の置換基で任意選択的に置換されてもよい；
（Ｇ） Ｒ^１３およびＲ^１４は各々独立してＨ、（Ｃ_１−Ｃ_４）アルキル、（Ｃ_２−Ｃ_４）アルケニル、（Ｃ_１−Ｃ_４）ハロアルキル、（Ｃ_１−Ｃ_４）アルコキシ、および（Ｃ_１−Ｃ_４）ハロアルコキシからなる群から選択される；
（Ｈ） Ｘは、Ｃ、ＳおよびＰ（Ｃ_１〜Ｃ_６）アルキルからなる群から選択される；
（Ｉ） ｎは、１または２である；
（Ｊ） Ｒ^１５は、（Ｃ_１−Ｃ_４）アルキル、（Ｃ_２−Ｃ_４）アルケニル、（Ｃ_１−Ｃ_４）ハロアルキル、（Ｃ_１−Ｃ_４）アルコキシ、（Ｃ_１−Ｃ_４）ハロアルコキシ、フェニル、およびＮＨ（Ｃ_１−Ｃ_４）ハロアルキルからなる群から選択され、
式中、アルキル、アルケニル、ハロアルキル、アルコキシ、ハロアルコキシ、およびフェニルの各々は、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、およびＯＨからなる群から独立して選択される１個以上の置換基で任意で置換されてもよい；および
式１の分子の農学的に許容可能な酸付加塩、塩誘導体、溶媒和物、エステル誘導体、結晶多形体、同位体、分割立体異性体、および互変異性体を開示するものである。 This document describes the numerator of formula 1.

During the ceremony:
(A) R ¹ , R ⁵ , R ⁶ , R ¹¹ and R ¹² are independently H, F, Cl, Br, I, CN, (C _1- C ₄ ) alkyl, (C _1- C _4). ) Haloalkyl, selected from the group consisting of _{(C 1-} C ₄ ) alkoxy, and (C _1- C _{4) haloalkoxy;}
^{(B) R} 2, R ³ and ^{R 4} are each independently H, F, Cl, Br, I, CN, (C 1 ~C 4) _{alkyl, (C} 2 _{~C 4)} alkenyl, _{(C 2} Selected from the group consisting of ~ C ₄ ) alkynyl, (C ₁ ~ C ₄ ) haloalkyl, (C ₁ ~ C ₄ ) alkoxy and (C ₁ ~ C _{4) haloalkoxy;}
(C) R ⁷ is (C _1- C ₆ ) haloalkyl;
(D) R ⁹ is (F), H, F, Cl, Br, I, CN, (C _1- C ₄ ) alkyl, (C _1- C ₄ ) haloalkyl, (C _1- C ₄ ) alkoxy, And (C _1- C ₄ ) selected from the group consisting of haloalkoxy;
^{(E) R 10} is, (F), F, Cl , Br, I, CN, (C 1 ~C 4) _{alkyl, (C} 2 _{~C 4) alkenyl, (C} 2 _{~C 4)} alkynyl, (C Selected from the group consisting of _{1 to} C ₄ ) haloalkyl, (C _{1 to} C ₄ ) alkoxy, and (C _{1 to} C _{4) haloalkoxy.}
(F) Both R ⁹ and R ¹⁰ can optionally form a 3- to 5-membered saturated or unsaturated hydrocarbyl ring.
The hydrocarbyl ring may be optionally substituted with one or more substituents independently selected from the group consisting of F, Cl, Br, I, and CN;
(G) R ¹³ and R ¹⁴ are independently H, (C _1- C ₄ ) alkyl, (C _2- C ₄ ) alkenyl, (C _1- C ₄ ) haloalkyl, (C _1- C ₄ ) alkoxy. , and _(C 1 -C ₄₎ is selected from the group consisting of haloalkoxy;
(H) X is selected from the group consisting of C, S and P (C _1- C _{6) alkyl;}
(I) n is 1 or 2;
(J) R ¹⁵ is (C _1- C ₄ ) alkyl, (C _2- C ₄ ) alkenyl, (C _1- C ₄ ) haloalkyl, (C _1- C ₄ ) alkoxy, (C _1- C ₄ ). haloalkoxy, phenyl, and NH _(C 1 -C ₄₎ is selected from the group consisting of haloalkyl,
In the formula, each of alkyl, alkenyl, haloalkyl, alkoxy, haloalkoxy, and phenyl is optional with one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, and OH. May be substituted with; and an agriculturally acceptable acid addition salt, salt derivative, solvate, ester derivative, crystalline polymorph, isotope, split steric isomer, and tautomer of the molecule of formula 1. Is disclosed.

In another embodiment, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are H. This embodiment may be used in combination with other embodiments of R ² , R ⁷ , R ¹⁰ , R ^{15, X, and n.}

In another embodiment, R ² is Cl, Br, or CH ₃ . Examples of this embodiment include R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , X, and n and others. It may be used in combination with the embodiment of.

In another embodiment, R ³ is F, Cl, Br or CH = CH ₂ . Other examples of this embodiment include R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , X, and n. It may be used in combination with the embodiment of.

In another embodiment, R ⁴ is Cl, Br, or CH ₃ . Other examples of this embodiment include R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , X, and n. May be used in combination with the embodiment of.

In another ^embodiment, R 2, ^{R 3,} and ^{R 4} is Cl. This embodiment is combined with other embodiments of R ¹ , R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , X, and n. You may use it.

In another embodiment, R ⁷ is (C _1- C ₆ ) haloalkyl. Other examples of this embodiment include R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , X, and n. It may be used in combination with the embodiment of.

In another embodiment, R ⁷ is CF ₃ or CF ₂ CH ₃ . Other examples of this embodiment include R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , X, and n. It may be used in combination with the embodiment of.

In another embodiment, R ¹⁰ is Cl, Br, I, CH ₃ , or CF ₃ . Other examples of this embodiment include R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , X, and n. It may be used in combination with the embodiment of.

In another embodiment, R ¹³ or R ¹⁴ is CH ₃ . This embodiment is combined with other embodiments of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹¹ , R ¹² , R ¹⁵ , X, and n. You may use it.

In another embodiment, X is C or S. This ^{embodiment, R 1, R 2, R} 3, R 4, R 5, R 6, R 7, R 9, R 10, R 11, R 12, R 13, R 14, R 15, and n It may be used in combination with other embodiments.

In another embodiment, n is 1 or 2. This ^embodiment, of ^{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R 9, R 10, R 11, R 12, R 13, R 14, R 15, and X It may be used in combination with other embodiments.

In another embodiment, R ¹⁵ is CH ₂ CH ₂ CF ₃ or NHCH ₂ CF ₃ . Other examples of this embodiment include R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , X, and n. It may be used in combination with the embodiment of.

In another embodiment
(A) R ¹ , R ⁵ , R ⁶ , R ¹¹ and R ¹² are H;
(B) R ² , R ³ , and R ⁴ are independently H, F, Cl, Br, I, (C _1- C ₄ ) alkyl, (C _2- C ₄ ) alkenyl, and (C _{1-), respectively.} C ₄ ) Selected from the group consisting of haloalkyl;
(C) R ⁷ is (C _1- C ₆ ) haloalkyl;
(D) R ⁹ is H;
^{(E) R 10} is, H, F, Cl, Br, _I, is selected from the group consisting of _(C 1 _{~C 4)} alkyl, and _(C 1 _{~C 4)} haloalkyl;
^{(G) R 13} and ^{R 14} H and each independently is _(C 1 -C ₄₎ is selected from the group consisting of alkyl;
(H) X is selected from the group consisting of C and S;
(I) n is 1 or 2; and (J) R ¹⁵ is selected from the group consisting of (C _1- C ₄ ) haloalkyl and NH (C _1- C _{4) haloalkyl.}

Preparation benzyl alcohol 1-3 halogenated benzyl, ^{wherein, R 1, R 2, R} 3, R 4, R 5, R 6, and ^{R 7} is as disclosed above, several methods Can be prepared in. Ketones 1-1, bromobenzene, for example, using a lithium base such as n- butyl lithium in a polar aprotic solvent, after preferably in diethyl ether and treated with about -78 ° C. ~ about 0 ° C., R ⁷ a _{C (O) O (C 1} -C 4) alkyl ester, wherein the ester ^{R 7} is as disclosed above, for example, ethyl 2,2-difluoro-propanoate (not shown) or the like It can be prepared by processing with. Ketones 1-1, ^{wherein, R 1, R 2, R} 3, R 4, R 5, and ^{R 7} is as disclosed above, a polar protic solvent, preferably methanol, for example, hydroxide Treatment at about −10 ° C. to about 10 ° C. with a reducing agent such as sodium borohydride in the presence of a base such as an aqueous sodium solution gives benzyl alcohol 1-3 (Scheme 1, step a). Alternatively, for aldehyde 1-2, in the formula, R ⁶ is H, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as disclosed above, and polar aprotic solvents are preferred. Reacts with trifluorotrimethylsilane in tetrahydrofuran in the presence of a catalytic amount of tetrabutylammonium fluoride (Scheme 1, step b) ^{to give R 7} the CF ₃ benzyl alcohol 1-3 in the formula. Can be done. Subsequently, benzyl alcohol 1-3 in the formula, where E is Br, Cl, or I, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are disclosed above. Reacts with a halogenating reagent, such as N-bromosuccinimide, in a solvent that does not react with the reagent, preferably in dichloromethane, at about 40 ° C., as is, with triethyl phosphite. By doing so, benzyl halide 1-4 in which E is Br in the formula is obtained (Scheme 1, step c). Alternatively, benzyl alcohol 1-3 is treated with a sulfonyl chloride such as methanesulfonyl chloride in the presence of a base such as trimethylamine and then the resulting sulfonate is transferred to a transition such as iron (III) bromide. By treatment with a metal bromide, E can be converted to Br, benzyl halide 1-4 in the formula. Further, by treating with a chlorinating reagent such as thionyl chloride at about 110 ° C. in a hydrocarbon solvent such as toluene, for example, in the presence of a base such as pyridine, E is Cl in the formula, benzyl halide. 1-4 are obtained (scheme 1, step c).

フッ素化ビニル安息香酸エステル類及び酸類の調製
式中、Ｒ^９、Ｒ^１０、Ｒ^１１、及びＲ^１２は上記に開示した通りであるハロ安息香酸類２−１を、式中、Ｒ^９、Ｒ^１０、Ｒ^１１、及びＲ^１２は上記に開示した通りであるハロ安息香酸エステル類２−２に変換することができる。ハロ安息香酸類２−１を、たとえばエタノールなどの（Ｃ_１−Ｃ_８）アルコールの存在下、たとえば硫酸などの酸で処理することにより、ハロ安息香酸エチルエステル類２−２が得られる（スキーム２、工程ａ）。フッ素化ビニル安息香酸エステル類２−３は、極性非プロトン性溶媒、好ましくは１，３−ジメチル−２−イミダゾリジノン中、ほぼ周囲温度〜約４５℃の温度範囲で、たとえばテトラキス（トリフェニルホスフィン）パラジウム（０）などのパラジウム触媒、たとえばヨウ化銅（Ｉ）などの銅添加物、およびたとえばフッ化セシウムなどのフッ化物源の存在下、２−２とフッ素化ビニルシランを反応させることにより利用可能となり、フッ素化ビニル安息香酸エステル類２−３が得られる（スキーム２、工程ｂ）。フッ素化ビニル安息香酸エステル類２−３を、極性非プロトン性溶媒、好ましくはテトラヒドロフランと、極性プロトン性溶媒、好ましくはメタノールおよび水を含む混合溶媒系中、ほぼ周囲温度で、たとえば水酸化リチウムなどの水酸化金属源で処理すると、フッ素化ビニル安息香酸類２−４を得ることができる（スキーム２、工程ｃ）。 Scheme 1

Preparation of Vinyl Fluorinated Vinyl Benzoic Acid Esters and Acids In the formula, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are halobenzoic acids 2-1 as disclosed above, in the formula R ⁹ , R ¹⁰ , R ¹¹ and R ¹² can be converted to halobenzoic acid esters 2-2 as disclosed above. Halo benzoic acids 2-1, for example in the presence of (C 1 _{-C 8)} alcohols such as ethanol, for example, by treatment with an acid such as sulfuric acid, halobenzoic acid ethyl ester 2-2 is obtained (Scheme 2 , Step a). Fluorinated vinyl benzoic acid esters 2-3 are contained in a polar aproton solvent, preferably 1,3-dimethyl-2-imidazolidinone, in a temperature range of approximately ambient temperature to about 45 ° C., for example tetrakis (triphenyl). By reacting 2-2 with vinyl fluorinated silane in the presence of a palladium catalyst such as phosphine) palladium (0), a copper additive such as copper (I) iodide, and a fluoride source such as cesium fluoride. It becomes available and fluorinated vinyl benzoic acid esters 2-3 are obtained (Scheme 2, step b). Vinyl fluorinated benzoic acid esters 2-3 in a mixed solvent system containing polar aprotic solvents, preferably tetrahydrofuran, and polar protic solvents, preferably methanol and water, at approximately ambient temperature, such as lithium hydroxide, etc. When treated with the metal hydroxide source of the above, vinyl fluorinated benzoic acids 2-4 can be obtained (scheme 2, step c).

あるいは、ハロ安息香酸類２−１を、極性非プロトン性溶媒、好ましくはジメチルスルホキシド中、約８０℃〜約１４０℃の温度範囲で、たとえば１，１’−ビス（ジフェニルホスフィノ）フェロセンパラジウム（ＩＩ）ジクロリドなどのパラジウム触媒と、たとえば炭酸カリウムなどの塩基の存在下、たとえばビニルトリフルオロボラートまたは３−ヒドロキシ−２，３−ジメチルブタン−２−イル水素ビニルボロナートなどのビニルボラン源で直接処理することにより、ビニル安息香酸類３−１を得ることができ、式中、Ｒ^９、Ｒ^１０、Ｒ^１１、およびＲ^１２は上記に開示した通りである（スキーム３、工程ａ）。ビニル安息香酸類３−１を、極性非プロトン性溶媒、好ましくはジクロロメタン中で、たとえばＮ−ブロモスクシンイミドなどの臭素源、およびたとえばトリエチルアミントリヒドロフルオライドなどのフッ素源を用いて約０℃で処理することにより、ブロモフルオロアルキル安息香酸類３−２を得ることができ、式中、Ｒ^９、Ｒ^１０、Ｒ^１１、およびＲ^１２は上記で開示した通りである（スキーム３、工程ｂ）。ブロモフルオロアルキル安息香酸類３−２を、極性プロトン性溶媒、好ましくはメタノール中、約０℃〜ほぼ周囲温度の温度範囲で、たとえばカリウムｔｅｒｔ−ブトキシドなどの塩基で処理すると、フッ素化ビニル安息香酸類２−４を得ることができる（スキーム３、工程ｃ）。 Scheme 2

Alternatively, halobenzoic acids 2-1 are placed in a polar aprotic solvent, preferably dimethyl sulfoxide, in a temperature range of about 80 ° C to about 140 ° C, for example 1,1'-bis (diphenylphosphino) ferrocene palladium (II). ) Direct treatment with a palladium catalyst such as dichloride and a vinylboran source such as vinyltrifluoroborate or 3-hydroxy-2,3-dimethylbutane-2-ylhydrogenvinylboronate in the presence of a base such as potassium carbonate. Thereby, vinyl benzoic acids 3-1 can be obtained, and in the formula, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are as disclosed above (Scheme 3, step a). Vinyl benzoic acids 3-1 are treated in a polar aprotic solvent, preferably dichloromethane, at about 0 ° C. with a bromine source such as N-bromosuccinimide and a fluorine source such as triethylamine trihydrofluoride. Thereby, the bromofluoroalkyl benzoic acids 3-2 can be obtained, and in the formula, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are as disclosed above (Scheme 3, step b). When bromofluoroalkyl benzoic acids 3-2 are treated with a base such as potassium tert-butoxide in a polar protic solvent, preferably methanol, in a temperature range of about 0 ° C. to approximately ambient temperature, vinyl fluorinated benzoic acids 2 -4 can be obtained (Scheme 3, step c).

フッ素化フェニルアリル安息香酸の調製
ハロゲン化ベンジル１−４及びフッ素化ベンジル安息香酸２−４を、極性非プロトン性溶媒、好ましくはＮ−メチル−２−ピロリドン中、約１００℃〜約１８０℃の温度で、たとえば塩化銅（Ｉ）または臭化銅（Ｉ）などの銅（Ｉ）源、およびたとえば２，２−ビピリジルなどのピリジンリガンドで処理すると、フッ素化フェニルアリル安息香酸４−１を得ることができ、式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^９、Ｒ^１０、Ｒ^１１、及びＲ^１２は上記に開示した通りである（スキーム４、工程ａ）。 Scheme 3

Preparation of Fluorinated Phenylallyl Benzoic Acid benzyl halide 1-4 and benzyl fluorinated benzoic acid 2-4 in a polar aprotic solvent, preferably N-methyl-2-pyrrolidone, at about 100 ° C to about 180 ° C. Treatment at temperature with a copper (I) source, such as copper (I) chloride or copper (I) bromide, and a pyridine ligand, such as 2,2-bipyridyl, gives 4-1 fluorinated phenylallyl benzoic acid. In the equation, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are as disclosed above (scheme). 4, step a).

フッ素化フェニルアリルベンズアミド類の調製
フェニルアリルベンズアミド類５−３は、式中、Ｒ^１３はＨであり、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１４、Ｘ、ｎ、およびＲ^１５は上記に開示されるとおりであり、式中、Ｒ^１４、Ｘ、ｎ、およびＲ^１５が上記に開示されるとおりであるアミン類またはアミン塩類５−２と、式中、Ａは活性化基であり、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^９、Ｒ^１０、Ｒ^１１、およびＲ^１２は上記に開示される通りである活性カルボン酸５−１を、無水極性非プロトン性溶媒、好ましくはジクロロメタン、テトラヒドロフラン、１，２−ジクロロエタンまたはＮ，Ｎ−ジメチルホルムアミド中、約０℃〜約１２０℃の温度で、たとえばトリエチルアミン、ジイソプロピルエチルアミン、または４−メチルモルホリンなどの塩基を用いて処理することにより調製されることができる（スキーム５、工程ａ）。 Scheme 4

Preparation phenylallyl benzamide compounds 5-3 fluorinated phenyl allyl benzamide compounds are those ^{wherein, R 13} is ^{H, R 1, R 2,} R 3, R 4, R 5, R 6, R 7, R 9 , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , X, n, and R ¹⁵ are as disclosed above, and in the formula, R ¹⁴ , X, n, and R ¹⁵ are as disclosed above. with an amine or amine salt 5-2 is, in the formula, a is an activating ^{group, R 1, R 2, R} 3, R 4, R 5, R 6, R 7, R 9, R 10, R ¹¹ and R ¹² contain the active carboxylic acid 5-1 as disclosed above in an anhydrous polar aprotic solvent, preferably dichloromethane, tetrahydrofuran, 1,2-dichloroethane or N, N-dimethylformamide. It can be prepared by treatment at a temperature of about 0 ° C. to about 120 ° C. with a base such as, for example, triethylamine, diisopropylethylamine, or 4-methylmorpholine (Scheme 5, step a).

活性カルボン酸類５−１は、酸塩化物、酸臭化物、もしくは酸フッ化物などの酸ハロゲン化物；パラニトロフェニルエステル、ペンタフルオロフェニルエステル、エチル（ヒドロキシイミノ）シアノ酢酸エステル、メチルエステル、エチルエステル、ベンジルエステル、Ｎ−ヒドロキシスクシンイミジルエステル、ヒドロキシベンゾトリアゾール−１−イルエステル、もしくはヒドロキシピリジルトリアゾール−１−イルエステルなどのカルボン酸エステル；Ｏ−アシルイソ尿素；酸無水物；またはチオエステルであってもよい。酸塩化物類５−１は、たとえば塩化オキサリルまたは塩化チオニルなどの脱水塩素化試薬により処理することで、対応するカルボン酸類から調製されることができる。活性カルボン酸類５−１は、ｉｎ ｓｉｔｕで、たとえば１−［ビス（ジメチルアミノ）メチレン］−１Ｈ−１，２，３−トリアゾロ［４，５−ｂ］ピリジニウム３−オキシドヘキサフルオロホスフェート（ＨＡＴＵ）、Ｏ−（ベンゾトリアゾール−１−イル）−Ｎ，Ｎ，Ｎ′，Ｎ′−テトラメチルウロニウムヘキサフルオロホスフェート（ＨＢＴＵ）、または（１−シアノ−２−エトキシ−２−オキソエチリデンアミノオキシ）ジメチルアミノ−モルホリノ−カルベニウムヘキサフルオロホスフェート（ＣＯＭＵ）などのウロニウム塩を用いてカルボン酸類から調製されることができる。また活性カルボン酸類５−１は、ｉｎ ｓｉｔｕで、たとえばベンゾトリアゾール−１−イル−オキシトリピロリジノホスホニウムヘキサフルオロホスフェート（ＰｙＢｏｐ）などのホスホニウム塩を用いてカルボン酸類から調製されることもできる。さらに活性カルボン酸類５−１は、ｉｎ ｓｉｔｕで、たとえばヒドロキシベンゾトリアゾール・一水和物（ＨＯＢｔ）または１−ヒドロキシ−７−アザベンゾトリアゾール（ＨＯＡｔ）などのトリアゾールの存在下、たとえば１−（３−ジメチルアミノプロピル）−３−エチルカルボジイミド（ＥＤＣ）、またはジシクロヘキシルカルボジイミド（ＤＣＣ）などのカップリング試薬を用いて、カルボン酸類から調製されることもできる。Ｏ−アシルイソ尿素類は、１−（３−ジメチルアミノプロピル）−３−エチルカルボジイミドまたはジシクロヘキシルカルボジイミドなどの脱水カルボジイミドを用いて調製され得る。また活性カルボン酸類５−１は、ｉｎ ｓｉｔｕで、たとえば１−ヒドロキシ−７−アザベンゾトリアゾール（ＨＯＡｔ）などのトリアゾールの存在下、たとえば２−クロロ−１，３−ジメチルイミダゾリジニウムヘキサフルオロホスフェート（ＣＩＰ）などのカップリング試薬を用いてカルボン酸類から調製されることもできる。 Scheme 5

Active carboxylic acids 5-1 are acid halides such as acidifieds, acid bromides, or acid fluorides; paranitrophenyl esters, pentafluorophenyl esters, ethyl (hydroxyimino) cyanoacetate esters, methyl esters, ethyl esters, Carboxylic acid esters such as benzyl ester, N-hydroxysuccinimidyl ester, hydroxybenzotriazole-1-yl ester, or hydroxypyridyltriazole-1-yl ester; O-acylisourea; acid anhydride; or even thioester good. Acyl chlorides 5-1 can be prepared from the corresponding carboxylic acids by treatment with dehydration chlorination reagents such as oxalyl chloride or thionyl chloride. The active carboxylic acids 5-1 are in situ, for example 1- [bis (dimethylamino) methylene] -1H-1,2,3-triazolo [4,5-b] pyridinium 3-oxide hexafluorophosphate (HATU). , O- (benzotriazole-1-yl) -N, N, N', N'-tetramethyluronium hexafluorophosphate (HBTU), or (1-cyano-2-ethoxy-2-oxoethylideneaminooxy) It can be prepared from carboxylic acids using uronium salts such as dimethylamino-morpholino-carbenium hexafluorophosphate (COMU). Active carboxylic acids 5-1 can also be prepared in situ from carboxylic acids using, for example, phosphonium salts such as benzotriazole-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBop). In addition, the active carboxylic acids 5-1 are in situ, for example in the presence of triazoles such as hydroxybenzotriazole monohydrate (HOBt) or 1-hydroxy-7-azabenzotriazole (HOAt), eg 1- (3). It can also be prepared from carboxylic acids using coupling reagents such as −dimethylaminopropyl) -3-ethylcarbodiimide (EDC), or dicyclohexylcarbodiimide (DCC). O-acylisoureas can be prepared using dehydrated carbodiimides such as 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide or dicyclohexylcarbodiimide. The active carboxylic acids 5-1 are insitu, for example, in the presence of triazoles such as 1-hydroxy-7-azabenzotriazole (HOAt), for example 2-chloro-1,3-dimethylimidazolidinium hexafluorophosphate (2-chloro-1,3-dimethylimidazolidinium hexafluorophosphate). It can also be prepared from carboxylic acids using a coupling reagent such as CIP).

The amines or amine salts 5-2 can be made from the corresponding N-tert-butoxycarbonylamines by treatment with an acid such as hydrochloric acid in situ. Optionally, the amine is insitu before the reaction with the active carboxylic acid 5-1 or during the reaction with the active carboxylic acid 5-1 in the presence of a base such as sodium bicarbonate or triethylamine. A phenylallyl benzamide 5-3 can be obtained by free baseizing the salts 5-2.

Alternatively, fluorinated phenyl allylbenzamide acids 5-3, ^{wherein, R 13} is ^{H, R 1, R 2,} R 3, R 4, R 5, R 6, R 7, R 9, R 10, R ¹¹ , R ¹² and R ¹⁴ are amines or amine salts 6-1 as disclosed above, where A is the activating group and X, n and R ¹⁵ are disclosed above. The active carboxylic acid 6-2 as described above in an anhydrous polar aprotic solvent, preferably dichloromethane, tetrahydrofuran, 1,2-dichloroethane or N, N-dimethylformamide, at a temperature of about 0 ° C to about 120 ° C. It can be prepared by treatment with a base such as, for example, triethylamine, diisopropylethylamine, or 4-methylmorpholine (Scheme 6, step a). Fluorinated phenylallyl benzamides 5-3 are amines or amine salts 6-1 in the formula, where A is Cl, X is S, n is 2, and R ¹⁵ is disclosed above. At a temperature of about 0 ° C. to about 120 ° C. in an anhydrous polar aprotic solvent, preferably dichloromethane, tetrahydrofuran, 1,2-dichloroethane or N, N-dimethylformamide, using the same sulfonyl chloride 6-2. It can also be prepared by treatment in the presence of a base such as, for example, triethylamine, diisopropylethylamine, or 4-methylmorpholine (Scheme 6, step a).

活性カルボン酸類６−２は、たとえば酸塩化物、酸臭化物、もしくは酸フッ化物などの酸ハロゲン化物；たとえばパラ−ニトロフェニルエステル、ペンタフルオロフェニルエステル、エチル（ヒドロキシイミノ）シアノ酢酸エステル、メチルエステル、エチルエステル、ベンジルエステル、Ｎ−ヒドロキシスクシンイミジルエステル、ヒドロキシベンゾトリアゾール−１−イルエステル、もしくはヒドロキシピリジルトリアゾール−１−イルエステルなどのカルボン酸エステル；Ｏ−アシルイソ尿素；酸無水物；またはチオエステル；たとえばパラ−ニトロフェニルカルバミン酸エステルなどのカルバミン酸エステルであってもよい。酸塩化物類は、たとえば塩化オキサリルまたは塩化チオニルなどの脱水塩素化試薬により処理することで、対応するカルボン酸類から調製されることができる。活性カルボン酸類６−２は、ｉｎ ｓｉｔｕで、たとえば１−［ビス（ジメチルアミノ）メチレン］−１Ｈ−１，２，３−トリアゾロ［４，５−ｂ］ピリジニウム３−オキシドヘキサフルオロホスフェート（ＨＡＴＵ）、Ｏ−（ベンゾトリアゾール−１−イル）−Ｎ，Ｎ，Ｎ′，Ｎ′−テトラメチルウロニウムヘキサフルオロホスフェート（ＨＢＴＵ）、または（１−シアノ−２−エトキシ−２−オキソエチリデンアミノオキシ）ジメチルアミノ−モルホリノ−カルベニウムヘキサフルオロホスフェート（ＣＯＭＵ）などのウロニウム塩を用いてカルボン酸類から調製されることができる。また活性カルボン酸類６−２は、ｉｎ ｓｉｔｕで、たとえばベンゾトリアゾール−１−イル−オキシトリピロリジノホスホニウムヘキサフルオロホスフェート（ＰｙＢｏｐ）などのホスホニウム塩を用いてカルボン酸類から調製されることもできる。さらに、活性カルボン酸エステル類６−２は、ｉｎ ｓｉｔｕで、たとえばヒドロキシベンゾトリアゾール・一水和物（ＨＯＢｔ）または１−ヒドロキシ−７−アザベンゾトリアゾール（ＨＯＡｔ）などのトリアゾールの存在下、１−（３−ジメチルアミノプロピル）−３−エチルカルボジイミド（ＥＤＣ）、またはジシクロヘキシルカルボジイミド（ＤＣＣ）などのカップリング試薬を用いてカルボン酸類から調製されることもできる。Ｏ−アシルイソ尿素類は、１−（３−ジメチルアミノプロピル）−３−エチルカルボジイミド（ＥＤＣ）またはジシクロヘキシルカルボジイミド（ＤＣＣ）などの脱水カルボジイミドを用いて調製されることができる。また活性カルボン酸類６−２は、ｉｎ ｓｉｔｕで、たとえば１−ヒドロキシ−７−アザベンゾトリアゾール（ＨＯＡｔ）などのトリアゾールの存在下、たとえば２−クロロ−１，３−ジメチルイミダゾリジニウムヘキサフルオロホスフェート（ＣＩＰ）などのカップリング試薬を用いてカルボン酸類から調製されることもできる。 Scheme 6

Active carboxylic acids 6-2 are, for example, acid halides, acid bromides, or acid halides such as acid fluorides; for example, para-nitrophenyl esters, pentafluorophenyl esters, ethyl (hydroxyimino) cyanoacetic acid esters, methyl esters, etc. Carboxyl esters such as ethyl esters, benzyl esters, N-hydroxysuccinimidyl esters, hydroxybenzotriazole-1-yl esters, or hydroxypyridyltriazole-1-yl esters; O-acylisourea; acid anhydrides; or thioesters; For example, it may be a carbamate ester such as para-nitrophenyl carbamate. Acyl chlorides can be prepared from the corresponding carboxylic acids by treatment with dehydration chlorinating reagents such as oxalyl chloride or thionyl chloride. The active carboxylic acids 6-2 are in situ, for example 1- [bis (dimethylamino) methylene] -1H-1,2,3-triazolo [4,5-b] pyridinium 3-oxide hexafluorophosphate (HATU). , O- (benzotriazole-1-yl) -N, N, N', N'-tetramethyluronium hexafluorophosphate (HBTU), or (1-cyano-2-ethoxy-2-oxoethylideneaminooxy) It can be prepared from carboxylic acids using uronium salts such as dimethylamino-morpholino-carbenium hexafluorophosphate (COMU). Active carboxylic acids 6-2 can also be prepared in situ from carboxylic acids using phosphonium salts such as, for example, benzotriazole-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBop). In addition, the active carboxylic acid esters 6-2 are 1-in situ in the presence of triazoles such as, for example, hydroxybenzotriazole monohydrate (HOBt) or 1-hydroxy-7-azabenzotriazole (HOAt). It can also be prepared from carboxylic acids using coupling reagents such as (3-dimethylaminopropyl) -3-ethylcarbodiimide (EDC) or dicyclohexylcarbodiimide (DCC). O-acylisoureas can be prepared using dehydrated carbodiimides such as 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide (EDC) or dicyclohexylcarbodiimide (DCC). The active carboxylic acids 6-2 are in situ, for example, in the presence of triazoles such as 1-hydroxy-7-azabenzotriazole (HOAt), for example 2-chloro-1,3-dimethylimidazolidinium hexafluorophosphate (2-chloro-1,3-dimethylimidazolidinium hexafluorophosphate). It can also be prepared from carboxylic acids using a coupling reagent such as CIP).

Amines or amine salts 6-1 can be made from the corresponding N-tert-butoxycarbonylamines by treatment with an acid such as hydrochloric acid in situ. Optionally, the amine is insitu before the reaction with the active carboxylic acid 6-2 or during the reaction with the active carboxylic acid 6-2, for example in the presence of a base such as sodium bicarbonate or triethylamine. By free-basizing the salts 6-1, phenylallyl benzamide 5-3 can be obtained.

For fluorinated phenylallylbenzamides 7-2, in the formula, R ¹³ is H, X is C, n is 1, R ¹⁵ is NH (C _1- C ₆ ) haloalkyl, and R. ^{1, R 2, R 3,} R 4, R 5, R 6, R 7, R 9, R 10, R 11, R 12, and ^{R 14} are as disclosed above, amines or amine salts 6-1, ^{wherein, R 15} is _{N (C} 1 -C ₆₎ isocyanate 7-1 haloalkyl, anhydrous polar aprotic solvent, preferably dichloromethane, tetrahydrofuran, 1,2-dichloroethane, N, N -Dimethylformamide or any combination thereof, which can be prepared by treatment at a temperature of about 0 ° C. to about 120 ° C. with a base such as triethylamine, diisopropylethylamine, or 4-methylmorpholine. Yes (Scheme 7, step a).

アミン類およびアミン塩類５−２の調製
アミン類およびアミン塩類５−２は、スキーム８に概説される経路により調製されてもよい。ヒドラジン類８−１は、式中、Ｒ^１３はＨであり、ＰＧは、たとえばベンジルオキシカルボニルなどの保護基であり、およびＲ^１４は上記に開示されるとおりであり、これを、たとえばトリエチルアミン、ジイソプロピルエチルアミン、または４−メチルモルホリンなどの塩基の存在下、たとえば重炭酸ジ−ｔｅｒｔ−ブチルなどのカルボン酸塩源を用いて処理し（スキーム８、工程ａ）、次いで、無水極性非プロトン性溶媒、好ましくはジクロロメタン、テトラヒドロフラン、１，２−ジクロロエタン、またはＮ，Ｎ−ジメチルホルムアミド中、約０℃〜約１２０℃の温度で、たとえば水素ガスおよびパラジウム炭素などの還元剤を用いて処理することにより、ヒドラジン類８−２を得ることができ、式中、Ｒ^１３はＨであり、Ｒ^１４は上記に開示されるとおりである（スキーム８、工程ｂ）。ヒドラジン類８−２を、たとえばトリエチルアミン、ジイソプロピルエチルアミン、または４−メチルモルホリンなどの塩基の存在下で、活性カルボン酸６−２で処理し（スキーム８、工程ｃ）、次いで無水極性非プロトン性溶媒、好ましくはジクロロメタン、テトラヒドロフラン、１，２−ジクロロエタン、またはＮ，Ｎ−ジメチルホルムアミド中、約０℃〜約１２０℃の温度で、たとえば塩酸などの酸を用いて処理することにより、アミン類またはアミン塩類５−２を得ることができる（スキーム８、工程ｄ）。 Scheme 7

Preparation of amines and amine salts 5-2 Amines and amine salts 5-2 may be prepared by the route outlined in Scheme 8. For hydrazines 8-1, in the formula, R ¹³ is H, PG is a protecting group such as benzyloxycarbonyl, and R ¹⁴ is as disclosed above, for example triethylamine. Treatment in the presence of a base such as diisopropylethylamine or 4-methylmorpholine with a carboxylate source such as di-tert-butyl bicarbonate (Scheme 8, step a) is then followed by an anhydrous polar aproton solvent. By treatment in dichloromethane, tetrahydrofuran, 1,2-dichloroethane, or N, N-dimethylformamide at a temperature of about 0 ° C to about 120 ° C, for example with a reducing agent such as hydrogen gas and palladium carbon. , Hydrazines 8-2 can be obtained, where R ¹³ is H and R ¹⁴ is as disclosed above (Scheme 8, step b). Hydradins 8-2 are treated with an active carboxylic acid 6-2 in the presence of a base such as, for example, triethylamine, diisopropylethylamine, or 4-methylmorpholin (Scheme 8, step c), followed by an anhydrous polar aprotic solvent. Amines or amines, preferably in dichloromethane, tetrahydrofuran, 1,2-dichloroethane, or N, N-dimethylformamide, by treatment with an acid such as hydrochloric acid at a temperature of about 0 ° C to about 120 ° C. Salts 5-2 can be obtained (Scheme 8, step d).

Alternatively, hydrazines 8-2 are treated with isocyanate 7-1 in the presence of a base such as, for example, triethylamine, diisopropylethylamine, or 4-methylmorpholine (Scheme 8, step e), followed by an anhydrous polar aprotic solvent. Hydrazines or salts thereof, preferably in dichloromethane, tetrahydrofuran, 1,2-dichloroethane, or N, N-dimethylformamide, at a temperature of about 0 ° C to about 120 ° C, by treatment with an acid such as hydrochloric acid, for example. 8-3 can be obtained (scheme 8, step d).

アミン類およびアミン塩類６−１の調製
活性カルボン酸５−１を、たとえばジイソプロピルエチルアミン、または４−メチルモルホリンなどのアミン塩基の存在下、式中、Ｒ^１３はＨであり、Ｒ^１４は上記に開示されるとおりであるアミン類またはアミン塩類９−１で処理し（スキーム９、工程ａ）、次いで無水極性非プロトン性溶媒、好ましくはジクロロメタン、テトラヒドロフラン、１，２−ジクロロエタン、またはＮ，Ｎ−ジメチルホルムアミド中、約０℃〜約１２０℃の温度で、たとえば塩酸などの酸を用いて処理することにより、アミン類およびアミン塩類６−１を得ることができる（スキーム９、工程ｂ）。 Scheme 8

^{Preparation of amines and amine salts 6-1 In the formula, R 13} is H and R ¹⁴ is described above in the presence of an active carboxylic acid 5-1 such as diisopropylethylamine or an amine base such as 4-methylmorpholin. Treated with amines or amine salts 9-1 as disclosed (Scheme 9, step a), then anhydrous polar aprotonic solvents, preferably dichloromethane, tetrahydrofuran, 1,2-dichloroethane, or N, N- Amines and amine salts 6-1 can be obtained by treatment in dimethylformamide at a temperature of about 0 ° C. to about 120 ° C. with an acid such as hydrochloric acid (Scheme 9, step b).

Scheme 9

This example is for purposes of illustration only and should not be construed as limiting this disclosure to the embodiments disclosed in this example.

Starting materials, reagents and solvents obtained from commercial raw materials were used without exposure purification. The anhydrous solvent was purchased as Sure / Seal ™ manufactured by Aldrich and used as it was. Melting points have been obtained and uncorrected with the Thomas Hoover Unimelt Capillary Melting Point Device or the OptiMelt Automatic Melting Point System manufactured by Stanford Research Systems. The examples using "room temperature" were carried out in a laboratory controlled by air conditioning at a temperature in the range of about 20 ° C. to about 24 ° C. Molecules are given known names named according to the naming program within ISIS Draw, ChemDraw, or ACD Name Pro. If such a program cannot name a molecule, it uses conventional naming conventions to refer to such molecule. ¹ H NMR spectrum data is recorded in ppm (δ) units and is recorded in 300 MHz, 400 MHz, 500 MHz, or 600 MHz; ¹³ C NMR spectrum data is in ppm (δ) units and is 75 Recorded at MHz, 100 MHz, or 150 MHz; ¹⁹ F NMR spectrum data was recorded in ppm (δ) and recorded at 376 MHz.

２５ｍＬ丸底フラスコに、Ｎ−メチルピロリドン（２．０ｍＬ）中、２，２’−ビピリジン（０．２５５ｇ、１．６３ｍｍｏｌ）、２−ブロモ−４−（１−フルオロビニル）安息香酸（Ｃ２４）（１．００ｇ、４．０８ｍｍｏｌ）、及び５−（１−ブロモ−２，２，２−トリフルオロエチル）−１，２，３−トリクロロベンゼン（２．７９ｇ、８．１６ｍｍｏｌ）を加えて、黄色溶液を得た。臭化銅（Ｉ）（０．１１７ｇ、０．８１６ｍｍｏｌ）を加え、反応混合物を５分間窒素でパージした。その後、反応物を１５０℃で３時間加熱した。反応混合物を氷水（１００ｍＬ）に注ぎ込んだ。水をろ過し、得られた黒色ゴム状物質を酢酸エチル（８００ｍＬ）に溶解させ、ブライン（２ｘ２００ｍＬ）及び水（２ｘ２００ｍＬ）で洗浄し、硫酸マグネシウムで乾燥して濾過し、濃縮して、表題化合物を褐色の油状物（１．４０ｇ、６４％）として得た：¹H NMR (400 MHz, CDCl₃) δ 8.03 (d, J = 8.2 Hz, 1H), 7.89 (d, J = 1.8 Hz, 1H), 7.59 (dd, J = 8.3, 1.8 Hz, 1H), 7.43 (s, 2H), 5.83 (dd, J = 32.4, 9.6 Hz, 1H), 4.60 (p, J = 8.8 Hz, 1H); ¹⁹F NMR (376 MHz, CDCl₃) δ -69.32 (d, J = 2.3 Hz), -108.70 - -119.01 (m); ESIMS m/z 505 ([M-H]^-)。 Example 1: (Z) -2-bromo-4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) benzoic acid Preparation of (C1)

2,2'-bipyridine (0.255 g, 1.63 mmol), 2-bromo-4- (1-fluorovinyl) benzoic acid (C24) in N-methylpyrrolidone (2.0 mL) in a 25 mL round bottom flask. (1.00 g, 4.08 mmol) and 5- (1-bromo-2,2,2-trifluoroethyl) -1,2,3-trichlorobenzene (2.79 g, 8.16 mmol) were added. A yellow solution was obtained. Copper (I) bromide (0.117 g, 0.816 mmol) was added and the reaction mixture was purged with nitrogen for 5 minutes. The reaction was then heated at 150 ° C. for 3 hours. The reaction mixture was poured into ice water (100 mL). Water was filtered and the resulting black rubbery material was dissolved in ethyl acetate (800 mL), washed with brine (2x200 mL) and water (2x200 mL), dried over magnesium sulfate, filtered and concentrated to give the title compound. Was obtained as a brown oil (1.40 g, 64%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.03 (d, J = 8.2 Hz, 1H), 7.89 (d, J = 1.8 Hz, 1H). ), 7.59 (dd, J = 8.3, 1.8 Hz, 1H), 7.43 (s, 2H), 5.83 (dd, J = 32.4, 9.6 Hz, 1H), 4.60 (p, J = 8.8 Hz, 1H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -69.32 (d, J = 2.3 Hz), -108.70 --- 119.01 (m); ESIMS m / z 505 ([MH] ^- ).

黄色の油状物（７．６ｇ、６８％）として単離した：¹H NMR (400 MHz, CDCl₃) δ 8.04 (d, J = 8.2 Hz, 1H), 7.99 - 7.94 (m, 1H), 7.84 (dd, J = 8.2, 1.8 Hz, 1H), 7.44 (s, 2H), 5.90 (dd, J = 32.4, 9.6 Hz, 1H), 4.62 (p, J = 8.9 Hz, 1H); ¹⁹F NMR (376 MHz, CDCl₃) δ -59.60, -69.28 (d, J = 2.3 Hz),
-112.11；ESIMS m/z 493 ([M-H]^-)。 The following compounds were prepared in a manner similar to the procedure outlined in Example 1:
(Z) -4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) -2- (trifluoromethyl) benzoic acid (C2)

Isolated as a yellow oil (7.6 g, 68%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.04 (d, J = 8.2 Hz, 1H), 7.99 --7.94 (m, 1H), 7.84 (dd, J = 8.2, 1.8 Hz, 1H), 7.44 (s, 2H), 5.90 (dd, J = 32.4, 9.6 Hz, 1H), 4.62 (p, J = 8.9 Hz, 1H); ¹⁹ F NMR ( 376 MHz, CDCl ₃ ) δ -59.60, -69.28 (d, J = 2.3 Hz),
-112.11; ESIMS m / z 493 ([MH] ^- ).

黄色の泡状物（０．６２８ｇ、６０％）として単離した：¹H NMR (400 MHz, CDCl₃) δ 8.00 (d, J = 8.2 Hz, 1H), 7.95 (d, J= 8.8 Hz, 1H), 7.81 (d, J = 8.3 Hz, 1H), 7.42 (s, 2H), 5.96 (dd, J= 33.6, 9.8 Hz, 1H), 4.29 (td, J = 14.3, 9.8 Hz, 1H), 1.65 (t, J = 18.4 Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ -59.61, -92.97 - -97.35 (m), -114.82; ESIMS m/z491 ([M-H]^-)。 (Z) -4- (1,4,4-trifluoro-3- (3,4,5-trichlorophenyl) penta-1-ene-1-yl) -2- (trifluoromethyl) benzoic acid (C3) )

Isolated as yellow foam (0.628 g, 60%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.00 (d, J = 8.2 Hz, 1H), 7.95 (d, J = 8.8 Hz, 1H), 7.81 (d, J = 8.3 Hz, 1H), 7.42 (s, 2H), 5.96 (dd, J = 33.6, 9.8 Hz, 1H), 4.29 (td, J = 14.3, 9.8 Hz, 1H), 1.65 (t, J = 18.4 Hz, 3H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -59.61, -92.97 --- 97.35 (m), -114.82; ESIMS m / z491 ([MH] ^- ).

白色の固形物（４．２７ｇ、８８％）として単離した：¹H NMR (400 MHz, CDCl₃) δ 8.07 (d, J = 8.2 Hz, 1H), 7.68 (d, J = 1.7 Hz, 1H), 7.54 (dd, J = 8.3, 1.8 Hz, 1H), 7.43 (s, 2H), 5.85 (dd, J = 32.4, 9.6 Hz, 1H), 4.60 (p, J = 8.8 Hz, 1H); ¹⁹F NMR (376 MHz, CDCl₃) δ -69.33 (d, J = 2.2 Hz), -112.18 (d, J= 2.4 Hz); ESIMS m/z 461 ([M-H]^-)。 (Z) -2-Chloro-4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) benzoic acid (C4)

Isolated as a white solid (4.27 g, 88%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.07 (d, J = 8.2 Hz, 1H), 7.68 (d, J = 1.7 Hz, 1H) ), 7.54 (dd, J = 8.3, 1.8 Hz, 1H), 7.43 (s, 2H), 5.85 (dd, J = 32.4, 9.6 Hz, 1H), 4.60 (p, J = 8.8 Hz, 1H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -69.33 (d, J = 2.2 Hz), -112.18 (d, J = 2.4 Hz); ESIMS m / z 461 ([MH] ^- ).

褐色のゴム状物（２．００ｇ、３７％）として単離した：ESIMS m/z 583 ([M-H]^-)。 (Z) -4- (3- (3,5-dibromo-4-chlorophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoromethyl) benzoic acid Acid (C5)

Isolated as a brown rubbery material (2.00 g, 37%): ESIMS m / z 583 ([MH] ^- ).

褐色のゴム状物（０．５０ｇ、４３％）として単離した：¹H NMR (400 MHz, DMSO-d₆) δ 13.9 (br s, 1H), 8.16 (s, 1H), 8.09 (d, J = 8.0 Hz, 1H), 7.92 (d, J = 8.0 Hz, 1H), 7.82 (s, 2H), 7.64 (t, J = 6.0 Hz, 1H), 6.90 (dd, J = 36.0, 10.4 Hz, 1H), 5.26 - 5.17 (m, 1H); IR (薄膜) 3416, 2926, 1716, 1119 cm^-1; ESIMS m/z 449 ([M+H]⁺)。 (Z) -4- (3- (3,5-dichlorophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoromethyl) benzoic acid (C6)

Isolated as brown rubber (0.50 g, 43%): ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 13.9 (br s, 1H), 8.16 (s, 1H), 8.09 (d, J = 8.0 Hz, 1H), 7.92 (d, J = 8.0 Hz, 1H), 7.82 (s, 2H), 7.64 (t, J = 6.0 Hz, 1H), 6.90 (dd, J = 36.0, 10.4 Hz, 1H), 5.26 --5.17 (m, 1H); IR (thin film) 3416, 2926, 1716, 1119 cm ^-1 ; ESIMS m / z 449 ([M + H] ⁺ ).

褐色のゴム状物（２．５０ｇ、５６％）として単離した：¹H NMR (300 MHz, DMSO-d₆) δ 13.9 (br s, 1H), 8.16 (s, 1H), 8.09 (d, J = 10.8 Hz, 1H), 8.08 (s, 1H), 7.92 (d, J = 8.1 Hz, 1H), 7.75 - 7.65 (m, 2H), 6.90 (dd, J = 36.0, 10.4 Hz, 1H), 5.22 - 5.16 (m, 1H); IR (薄膜) 3440, 2927, 1716, 1175 cm^-1; ESIMS m/z459 ([M-H]^-)。 (Z) -4- (3- (3,4-dichlorophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoromethyl) benzoic acid (C7)

Isolated as brown rubber (2.50 g, 56%): ¹ H NMR (300 MHz, DMSO-d ₆ ) δ 13.9 (br s, 1H), 8.16 (s, 1H), 8.09 (d, J = 10.8 Hz, 1H), 8.08 (s, 1H), 7.92 (d, J = 8.1 Hz, 1H), 7.75 --7.65 (m, 2H), 6.90 (dd, J = 36.0, 10.4 Hz, 1H), 5.22 --5.16 (m, 1H); IR (thin film) 3440, 2927, 1716, 1175 cm ^-1 ; ESIMS m / z 459 ([MH] ^- ).

褐色のゴム状物（２．２０ｇ、３９％）として単離した：¹H NMR (300 MHz, CDCl₃) δ 8.05 - 7.95 (m, 2H), 7.84 (d, J= 7.2 Hz, 1H), 7.69 - 7.68 (m, 1H), 7.49 (s, 2H), 5.95 (dd, J = 32.7, 9.6 Hz , 1H), 4.64 - 4.58 (p, 1H); IR (薄膜) 3439, 2925, 1714, 1118, 746 cm^-1; ESIMS m/z 549 ([M-H]^-)。 (Z) -4- (3- (3,5-dibromophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoromethyl) benzoic acid (C8) )

Isolated as a brown rubbery material (2.20 g, 39%): ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.05 --7.95 (m, 2H), 7.84 (d, J = 7.2 Hz, 1H), 7.69 --7.68 (m, 1H), 7.49 (s, 2H), 5.95 (dd, J = 32.7, 9.6 Hz, 1H), 4.64 --4.58 (p, 1H); IR (thin film) 3439, 2925, 1714, 1118 , 746 cm ^-1 ; ESIMS m / z 549 ([MH] ^- ).

褐色のゴム状物（１．２０ｇ、５４％）として単離した：¹H NMR (300 MHz, CDCl₃) δ 7.88 (s, 2H), 7.76 - 7.75 (m, 1H), 7.37 (d, J = 6.0 Hz, 2H), 5.90 (dd, J = 32.1, 9.0 Hz , 1H), 4.62 - 4.56 (p, 1H); IR (薄膜） 3445, 2926, 1698, 1260, 750 cm^-1; ESIMS m/z 477 ([M-H]^-)。 (Z) -4- (3- (3,5-dichloro-4-fluorophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoromethyl) Benzoic acid (C9)

Isolated as brown rubber (1.20 g, 54%): ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.88 (s, 2H), 7.76 --7.75 (m, 1H), 7.37 (d, J) = 6.0 Hz, 2H), 5.90 (dd, J = 32.1, 9.0 Hz, 1H), 4.62 --4.56 (p, 1H); IR (thin film) 3445, 2926, 1698, 1260, 750 cm ^-1 ; ESIMS m / z 477 ([MH] ^- ).

黄色のゴム状物（２．２０ｇ、５３％）として単離した：¹H NMR (300 MHz, CDCl₃) δ 8.01 (d, J = 8.1 Hz, 1H), 7.94 (s, 1H), 7.83 (d, J = 8.1 Hz, 1H), 7.11 (s, 2H), 6.00 (dd, J= 33.0, 9.9 Hz, 1H), 4.58 - 4.55 (m, 1H), 2.40 (s, 6H); IR (薄膜) 3445, 1713, 852 cm^-1; ESIMS m/z 453 ([M-H]^-)。 (Z) -4- (3- (4-Chloro-3,5-dimethylphenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoromethyl) Benzoic acid (C10)

Isolated as yellow rubber (2.20 g, 53%): ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.01 (d, J = 8.1 Hz, 1H), 7.94 (s, 1H), 7.83 ( d, J = 8.1 Hz, 1H), 7.11 (s, 2H), 6.00 (dd, J = 33.0, 9.9 Hz, 1H), 4.58 --4.55 (m, 1H), 2.40 (s, 6H); IR (thin film) ) 3445, 1713, 852 cm ^-1 ; ESIMS m / z 453 ([MH] ^- ).

淡褐色の固形物（１．５０ｇ、６５％）として単離した：融点78〜81℃；¹H NMR (300 MHz, CDCl₃) δ 8.09 - 7.99 (m, 2H), 7.83 - 7.81 (m, 1H), 7.42 (s, 2H), 5.95 (dd, J= 32.4 Hz, 9.6 Hz, 1H), 4.63 - 4.57 (m, 1H); IR (薄膜) 3445, 1713, 852 cm^-1; ESIMS m/z538 ([M+H]⁺)。 (Z) -4- (3- (4-Bromo-3,5-dichlorophenyl) -1,4,5,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoromethyl) benzoic acid Acid (C11)

Isolated as a light brown solid (1.50 g, 65%): melting point 78-81 ° C; ^{1 1} H NMR (300 MHz, CDCl ₃ ) δ 8.09 --7.99 (m, 2H), 7.83 --7.81 (m,) 1H), 7.42 (s, 2H), 5.95 (dd, J = 32.4 Hz, 9.6 Hz, 1H), 4.63 --4.57 (m, 1H); IR (thin film) 3445, 1713, 852 cm ^-1 ; ESIMS m / z538 ([M + H] ⁺ ).

褐色のゴム状物（２．０ｇ、６２％）として単離した：¹H NMR (300 MHz, DMSO-d₆) δ 13.80 (br s, 1H), 8.15 (s, 1H), 8.09 (d, J = 8.1 Hz, 1H), 7.93 - 7.78 (m, 4H), 6.91 (dd, J = 35.7, 10.2 Hz, 1H), 5.27 - 5.14 (m, 1H); IR (薄膜) 3081, 2927, 1714, 776 cm^-1; ESIMS m/z 503 ([M-H]^-)。 (Z) -4- (3- (3-Bromo-5-chlorophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoromethyl) benzoic acid ( C12)

Isolated as brown rubber (2.0 g, 62%): ¹ H NMR (300 MHz, DMSO-d ₆ ) δ 13.80 (br s, 1H), 8.15 (s, 1H), 8.09 (d, J = 8.1 Hz, 1H), 7.93 --7.78 (m, 4H), 6.91 (dd, J = 35.7, 10.2 Hz, 1H), 5.27 --5.14 (m, 1H); IR (thin film) 3081, 2927, 1714, 776 cm ^-1 ; ESIMS m / z 503 ([MH] ^- ).

黄色のゴム状物（２．１ｇ、７８％）として単離した：¹H NMR (400 MHz, CDCl₃) δ 8.02 (d, J = 8.4 Hz, 1H), 7.94 (s, 1H), 7.83 (d, J =8.4 Hz, 1H), 7.66 (d, J = 8.4 Hz, 2H), 7.26 - 7.21 (m, 1H), 5.96 (dd, J= 32.4, 9.2 Hz, 1H), 4.67 - 4.58 (p, 1H); IR (薄膜) 3426, 2925, 1714, 1115 cm^-1; ESIMS m/z547 ([M-H]^-)。 (Z) -4- (3- (3,4-dibromophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoromethyl) benzoic acid (C13) )

Isolated as yellow rubber (2.1 g, 78%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.02 (d, J = 8.4 Hz, 1H), 7.94 (s, 1H), 7.83 ( d, J = 8.4 Hz, 1H), 7.66 (d, J = 8.4 Hz, 2H), 7.26 --7.21 (m, 1H), 5.96 (dd, J = 32.4, 9.2 Hz, 1H), 4.67 --4.58 (p , 1H); IR (thin film) 3426, 2925, 1714, 1115 cm ^-1 ; ESIMS m / z547 ([MH] ^- ).

橙色の油状物（０．９４ｇ、６１％）として単離した：¹H NMR (400 MHz、CDCl₃) δ 8.09 (d、J = 8.8 Hz、1H)、7.49 - 7.45 (m、2H)、7.44 (s、2H)、5.80 (dd、J = 32.7、9.6 Hz、1H)、4.60 (p、J = 8.9 Hz、1H)、2.69 (s、3H); ¹⁹F NMR (376 MHz、CDCl₃) δ -69.40 (d、J = 2.3 Hz)、-108.40 - -115.65 (m); ESIMS m/z441 ([M-H]^-)。 (Z) -2-Methyl-4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) benzoic acid (C14)

Isolated as orange oil (0.94 g, 61%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.09 (d, J = 8.8 Hz, 1H), 7.49 --7.45 (m, 2H), 7.44 (s, 2H), 5.80 (dd, J = 32.7, 9.6 Hz, 1H), 4.60 (p, J = 8.9 Hz, 1H), 2.69 (s, 3H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -69.40 (d, J = 2.3 Hz), -108.40 --- 115.65 (m); ESIMS m / z441 ([MH] ^- ).

橙色の泡状物（０．２０４ｇ、５１％）として単離した：¹H NMR (400 MHz, CDCl₃) δ 8.07 (d, J = 8.8 Hz, 1H), 7.49 - 7.40 (m, 4H), 5.86 (dd, J = 33.9, 9.9 Hz, 1H), 4.27 (td, J= 14.3, 9.7 Hz, 1H), 2.68 (s, 3H), 1.65 (t, J = 18.4 Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ -95.11, -95.18, -114.57; ESIMS m/z437 ([M-H]^-)。 (Z) -2-Methyl-4- (1,4,4-trifluoro-3- (3,4,5-trichlorophenyl) penta-1-ene-1-yl) Benzoic acid (C15)

Isolated as orange foam (0.204 g, 51%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.07 (d, J = 8.8 Hz, 1H), 7.49 --7.40 (m, 4H), 5.86 (dd, J = 33.9, 9.9 Hz, 1H), 4.27 (td, J = 14.3, 9.7 Hz, 1H), 2.68 (s, 3H), 1.65 (t, J = 18.4 Hz, 3H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -95.11, -95.18, -114.57; ESIMS m / z437 ([MH] ^- ).

橙色の泡状物（０．１３６ｇ、６３％）として単離した：¹H NMR (400 MHz, CDCl₃) δ 7.99 (dd, J = 8.4, 4.0 Hz, 1H), 7.93 (s, 1H), 7.80 (d, J = 7.9 Hz, 1H), 7.42 (d, J = 2.6 Hz, 2H), 6.08 - 5.87 (m, 1H), 4.32 (td, J= 14.6, 9.8 Hz, 1H), 1.87 (ddt, J= 21.6, 15.4, 8.0 Hz, 2H), 1.07 (t, J= 7.4 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 170.72, 156.96 (d, J_CF = 253.0 Hz), 136.85, 135.06, 134.53, 133.75, 131.90, 131.19, 130.18, 129.17, 128.60, 128.05, 127.29, 124.11, 123.36 - 122.67 (m), 121.39, 104.66 (d, J_CF = 18.0 Hz), 46.46, 29.70 - 27.14 (m), 6.40 - 5.44 (m); ESIMS m/z 503 ([M-H]^-)。 (Z) -4- (1,4,4-trifluoro-3- (3,4,5-trichlorophenyl) hexa-1-ene-1-yl) -2- (trifluoromethyl) benzoic acid (C16) )

Isolated as orange foam (0.136 g, 63%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.99 (dd, J = 8.4, 4.0 Hz, 1H), 7.93 (s, 1H), 7.80 (d, J = 7.9 Hz, 1H), 7.42 (d, J = 2.6 Hz, 2H), 6.08 --- 5.87 (m, 1H), 4.32 (td, J = 14.6, 9.8 Hz, 1H), 1.87 (ddt) , J = 21.6, 15.4, 8.0 Hz, 2H), 1.07 (t, J = 7.4 Hz, 3H); ¹³ C NMR (101 MHz, CDCl ₃ ) δ 170.72, 156.96 (d, J _CF = 253.0 Hz), 136.85 , 135.06, 134.53, 133.75, 131.90, 131.19, 130.18, 129.17, 128.60, 128.05, 127.29, 124.11, 123.36 --122.67 (m), 121.39, 104.66 (d, J _CF = 18.0 Hz), 46.46, 29.70 --27.14 (m) ), 6.40 --5.44 (m); ESIMS m / z 503 ([MH] ^- ).

橙色のガラス状物（０．４９５ｇ、５１％）として単離した。¹H NMR (400 MHz, CDCl₃) δ 8.01 (d, J = 8.2 Hz, 1H), 7.94 (d, J= 1.6 Hz, 1H), 7.80 (dd, J = 8.2, 1.8 Hz, 1H), 7.49 (d, J = 2.1 Hz, 1H), 7.45 (d, J = 8.3 Hz, 1H), 7.26 7.22 (m, 1H), 6.00 (dd, J= 33.9, 9.8 Hz, 1H), 4.32 (ddd, J= 15.8, 13.0, 9.8 Hz, 1H), 1.62 (t, J= 18.4 Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ -59.58, -89.79 - -99.81 (m), -115.63; IR (薄膜) 3008, 1711 cm^-1; ESIMS m/z 455 ([M-H]^-)。 (Z) -4- (3- (3,4-dichlorophenyl) -1,4,4-trifluoropenta-1-ene-1-yl) -2- (trifluoromethyl) benzoic acid (C17)

It was isolated as an orange glassy substance (0.495 g, 51%). ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.01 (d, J = 8.2 Hz, 1H), 7.94 (d, J = 1.6 Hz, 1H), 7.80 (dd, J = 8.2, 1.8 Hz, 1H), 7.49 (d, J = 2.1 Hz, 1H), 7.45 (d, J = 8.3 Hz, 1H), 7.26 7.22 (m, 1H), 6.00 (dd, J = 33.9, 9.8 Hz, 1H), 4.32 (ddd, J = 15.8, 13.0, 9.8 Hz, 1H), 1.62 (t, J = 18.4 Hz, 3H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -59.58, -89.79 --- 99.81 (m), -115.63; IR (Thin film) 3008, 1711 cm ^-1 ; ESIMS m / z 455 ([MH] ^- ).

褐色のゴム状物（２．５ｇ、４６％）として単離した：¹H NMR (300 MHz, DMSO-d₆) δ 13.79 (br s, 1H), 8.15 - 8.06 (m, 3H), 7.91 (d, J = 8.1 Hz, 1H), 7.71 (s, 2H), 6.90 (dd, J = 36.0, 10.2 Hz, 1H), 5.21 - 5.15 (m, 1H); IR (薄膜) 3431, 2924, 1623, 597 cm^-1; ESIMS m/z503 ([M-H]^-)。 (Z) -4- (3- (3,4-dichlorophenyl) -1,4,4-trifluoropenta-1-ene-1-yl) -2- (trifluoromethyl) benzoic acid (C18)

Isolated as brown rubber (2.5 g, 46%): ¹ H NMR (300 MHz, DMSO-d ₆ ) δ 13.79 (br s, 1H), 8.15 --8.06 (m, 3H), 7.91 ( d, J = 8.1 Hz, 1H), 7.71 (s, 2H), 6.90 (dd, J = 36.0, 10.2 Hz, 1H), 5.21 --5.15 (m, 1H); IR (thin film) 3431, 2924, 1623, 597 cm ^-1 ; ESIMS m / z503 ([MH] ^- ).

黄色のゴム状物（１．５０ｇ、５７％）として単離した。¹H NMR (300 MHz, CDCl₃) δ 8.01 (d, J= 8.1 Hz, 2H) 7.94 (s, 2H), 7.76 - 7.75 (m, 1H), 7.37 (d, J = 6.0 Hz, 2H), 5.90 (dd, J = 32.1, 9.0 Hz, 1H); IR (薄膜）3445, 2926, 1698, 1260, 750 cm^-1; ESIMS m/z 443 ([M-H]^-)。 (Z) -4- (3- (3-Chloro-4-fluorophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoromethyl) benzoic acid (C19)

It was isolated as a yellow rubbery substance (1.50 g, 57%). ^{1 1} H NMR (300 MHz, CDCl ₃ ) δ 8.01 (d, J = 8.1 Hz, 2H) 7.94 (s, 2H), 7.76 --7.75 (m, 1H), 7.37 (d, J = 6.0 Hz, 2H), 5.90 (dd, J = 32.1, 9.0 Hz, 1H); IR (thin film) 3445, 2926, 1698, 1260, 750 cm ^-1 ; ESIMS m / z 443 ([MH] ^- ).

褐色のゴム状物（０．５０ｇ、４８％）として単離した：¹H NMR (300 MHz, CDCl₃) δ 8.03 (d, J = 8.1 Hz, 1H), 7.94 (s, 1H), 7.83 (d, J = 7.8 Hz, 1H), 7.46 - 7.44 (m, 1H), 7.23 - 7.13 (m, 2H), 5.98 (dd, J = 34.2, 9.9 Hz, 1H), 4.69 - 4.63 (m, 1H); IR (薄膜) 3092, 1751, 750 cm^-1; ESIMS m/z 443 ([M-H]^-)。 (Z) -4- (3- (4-Chloro-3-fluorophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoromethyl) benzoic acid (C20)

Isolated as brown rubber (0.50 g, 48%): ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.03 (d, J = 8.1 Hz, 1H), 7.94 (s, 1H), 7.83 ( d, J = 7.8 Hz, 1H), 7.46 --7.44 (m, 1H), 7.23 --7.13 (m, 2H), 5.98 (dd, J = 34.2, 9.9 Hz, 1H), 4.69 --4.63 (m, 1H) IR (thin film) 3092, 1751, 750 cm ^-1 ; ESIMS m / z 443 ([MH] ^- ).

黄色のゴム状物（１．１ｇ、５６％）として単離した：¹H NMR (400 MHz, CDCl₃) δ 8.15 (d, J = 8.2 Hz, 2H), 7.67 (d, J = 8.3 Hz, 2H), 7.44 (s, 2H), 5.84 (dd, J = 32.6, 9.6 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H); ¹⁹F NMR (376 MHz, CDCl₃) δ -69.38 (d, J = 2.2 Hz), -109.75 - -116.47 (m); ESIMS m/z 427 ([M-H]^-)。 (Z) -4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) benzoic acid (CC1)

Isolated as yellow rubber (1.1 g, 56%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.15 (d, J = 8.2 Hz, 2H), 7.67 (d, J = 8.3 Hz, 2H), 7.44 (s, 2H), 5.84 (dd, J = 32.6, 9.6 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -69.38 ( d, J = 2.2 Hz), -109.75 --- 116.47 (m); ESIMS m / z 427 ([MH] ^- ).

２５ｍＬバイアルに、（Ｚ）−２−ブロモ−４−（１，４，４，４−テトラフルオロ−３−（３，４，５−トリクロロフェニル）ブタ−１−エン−１−イル）安息香酸（Ｃ１）（０．５００ｇ、０．９８７ｍｍｏｌ）、ヨウ化銅（Ｉ）（０．００９４０ｇ、０．０４９０ｍｍｏｌ）、及び１，４−ジオキサン（４．９ｍＬ）を加えて、黄色懸濁液を形成させた。ヨウ化ナトリウム（０．２９６ｇ、１．９７ｍｍｏｌ）及びトランス−Ｎ，Ｎ′−ジメチルクロロヘキサン−１，２−ジアミン（０．０１４０ｇ、０．０９９０ｍｍｏｌ）を加え、反応混合物を１１０℃にて３．５時間撹拌した。反応混合物を濃縮し、フラッシュカラムクロマトグラフィで精製して、表題化合物を褐色の油状物（０．２４７ｇ、４３％）として得た：¹H NMR (300 MHz, CDCl₃) δ 8.21 (d, J = 1.7 Hz, 1H), 8.02 (d, J = 8.2 Hz, 1H), 7.62 (dd, J = 8.3, 1.7 Hz, 1H), 7.43 (s, 2H), 5.82 (dd, J = 32.5, 9.6 Hz, 1H), 4.59 (p, J = 8.9 Hz, 1H); ¹⁹F NMR (471 MHz, CDCl₃) δ -69.32, -112.14 (d, J = 20.8 Hz); ESIMS m/z553
([M-H]^-)。 Example 2: (Z) -2-iodo-4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) porcine-1-en-1-yl) benzoic acid Preparation of (C21)

In a 25 mL vial, (Z) -2-bromo-4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) benzoic acid (C1) (0.500 g, 0.987 mmol), copper (I) iodide (0.00940 g, 0.0490 mmol), and 1,4-dioxane (4.9 mL) were added to form a yellow suspension. I let you. Sodium iodide (0.296 g, 1.97 mmol) and trans-N, N'-dimethylchlorohexane-1,2-diamine (0.0140 g, 0.0990 mmol) were added, and the reaction mixture was added at 110 ° C. to 3. The mixture was stirred for 5 hours. The reaction mixture was concentrated and purified by flash column chromatography to give the title compound as a brown oil (0.247 g, 43%): ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.21 (d, J =). 1.7 Hz, 1H), 8.02 (d, J = 8.2 Hz, 1H), 7.62 (dd, J = 8.3, 1.7 Hz, 1H), 7.43 (s, 2H), 5.82 (dd, J = 32.5, 9.6 Hz, 1H), 4.59 (p, J = 8.9 Hz, 1H); ¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -69.32, -112.14 (d, J = 20.8 Hz); ESIMS m / z 553
([MH] ^- ).

テトラキス（トリフェニルホスフィン）パラジウム（０）（０．３０ｇ、０．２６ｍｍｏｌ）を、室温で、（Ｚ）−４−（３−（４−ブロモ−３，５−ジクロロフェニル）−１，４，４，４−テトラフルオロブタ−１−エン−１−イル）−２−（トリフルオロメチル）安息香酸（Ｃ１１）（１．４ｇ、２．６ｍｍｏｌ）のトルエン（１０ｍＬ）溶液に加えた。反応混合物を窒素でパージして脱気した（３ｘ１０分）。トリブチルビニルスタンナン（０．８２ｇ、２．６ｍｍｏｌ）を反応混合物に加えた。反応混合物を再び窒素でパージして脱気し（３ｘ１０分）、１２０℃で３時間撹拌した。反応混合物を水でクエンチした後、酢酸エチルで抽出した。有機層を硫酸ナトリウム上で乾燥させ、濾過し、濃縮した。３０％酢酸エチル／ヘキサン類を使用したフラッシュカラムクロマトグラフィで精製することにより、表題化合物を淡黄色のガム状物（０．８０ｇ、６３％）として得た：¹H NMR (300 MHz, CDCl₃) δ 7.85 (s, 1H), 7.82 (d, J = 8.4 Hz, 1H), 7.74 (d, J = 8.4 Hz, 1H), 7.42 (s, 1H), 7.37 (s, 1H), 6.72 - 6.65 (dd, J = 17.6 Hz, 11.6 Hz, 1H ), 5.86 - 5.73 (m, 3H), 4.61 - 4.56 (m, 1H); IR (薄膜) 3445, 2925, 1646, 1275, 749 cm^-1; ESIMS m/z 488 ([M+H]⁺)。 Example 3: (Z) -2-iodo-4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) benzoic acid Preparation of (C22)

Tetrakis (triphenylphosphine) palladium (0) (0.30 g, 0.26 mmol) at room temperature (Z) -4- (3- (4-bromo-3,5-dichlorophenyl) -1,4,4 , 4-Tetrafluorobuta-1-en-1-yl) -2- (trifluoromethyl) benzoic acid (C11) (1.4 g, 2.6 mmol) was added to a solution of toluene (10 mL). The reaction mixture was purged with nitrogen and degassed (3x10 min). Tributylvinyl stannan (0.82 g, 2.6 mmol) was added to the reaction mixture. The reaction mixture was purged with nitrogen again and degassed (3x10 min) and stirred at 120 ° C. for 3 hours. The reaction mixture was quenched with water and then extracted with ethyl acetate. The organic layer was dried over sodium sulfate, filtered and concentrated. Purification by flash column chromatography using 30% ethyl acetate / hexanes gave the title compound as a pale yellow gum (0.80 g, 63%): ¹ H NMR (300 MHz, CDCl ₃ ). δ 7.85 (s, 1H), 7.82 (d, J = 8.4 Hz, 1H), 7.74 (d, J = 8.4 Hz, 1H), 7.42 (s, 1H), 7.37 (s, 1H), 6.72 --6.65 ( dd, J = 17.6 Hz, 11.6 Hz, 1H), 5.86 --5.73 (m, 3H), 4.61 --4.56 (m, 1H); IR (thin film) 3445, 2925, 1646, 1275, 749 cm ^-1 ; ESIMS m / z 488 ([M + H] ⁺ ).

２５ｍＬバイアルに、ジクロロメタン（１．３ｍＬ）中、（Ｚ）−４−（１，４，４，４−テトラフルオロ−３−（３，４，５−トリクロロフェニル）ブタ−１−エン−１−イル）−２−（トリフルオロメチル）安息香酸（Ｃ２）（０．２００ｇ、０．４０４ｍｍｏｌ）、塩化オキサリル（０．０９５ｍＬ、１．０９ｍｍｏｌ）、及びＮ，Ｎ−ジメチルホルムアミド（触媒量）を加えて、黄色溶液を得た。反応物を室温で１５時間攪拌した。溶媒を真空下で除去し、表題化合物を黄色ゴム状物（０．２２０ｇ、９５％）として得た：¹H NMR (400 MHz, CDCl₃) δ 7.99 (d, J = 8.2 Hz, 1H), 7.92 (d, J = 1.7 Hz, 1H), 7.81 (dd, J = 8.2, 1.8 Hz, 1H), 7.44 (s, 2H), 5.88 (dd, J = 32.5, 9.6 Hz, 1H), 4.73 - 4.50 (m, 1H); ¹⁹F NMR (376 MHz, CDCl₃) δ -59.58, -69.32, -109.75 - -113.19 (m); IR (薄膜) 3445, 2925, 1646, 1275, 749 cm^-1; ESIMS m/z 476 ([M-Cl]⁺)。 Example 4: (Z) -4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) -2- (trifluoro) Preparation of Methyl) Benzoyl Chloride (C23)

In a 25 mL vial in dichloromethane (1.3 mL), (Z) -4- (1,4,5,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1- Il) -2- (trifluoromethyl) benzoic acid (C2) (0.200 g, 0.404 mmol), oxalyl chloride (0.095 mL, 1.09 mmol), and N, N-dimethylformamide (catalytic amount) were added. To obtain a yellow solution. The reaction was stirred at room temperature for 15 hours. The solvent was removed under vacuum to give the title compound as a yellow rubbery material (0.220 g, 95%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.99 (d, J = 8.2 Hz, 1 H),. 7.92 (d, J = 1.7 Hz, 1H), 7.81 (dd, J = 8.2, 1.8 Hz, 1H), 7.44 (s, 2H), 5.88 (dd, J = 32.5, 9.6 Hz, 1H), 4.73 --4.50 (m, 1H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -59.58, -69.32, -109.75 --- 113.19 (m); IR (thin film) 3445, 2925, 1646, 1275, 749 cm ^-1 ; ESIMS m / z 476 ([M-Cl] ⁺ ).

２５０ｍＬの丸底フラスコに、２−ブロモ−４−（１−フルオロビニル）安息香酸メチル（Ｃ２９）（１．８ｇ、７．０ｍｍｏｌ）、水酸化リチウム水和物（０．８８ｇ、２１ｍｍｏｌ）、メタノール（７．０ｍＬ）、テトラヒドロフラン（２１ｍＬ）、及び水（７．０ｍＬ）を加え、反応混合物を室温で一晩撹拌した。混合物を濃縮し、ｐＨ４の緩衝液でクエンチし、酢酸エチルで抽出して、表題化合物を白色固形物（１．０ｇ、５６％）として得た：¹H NMR (400 MHz, CDCl₃) δ 8.01 (d, J = 8.2 Hz, 1H), 7.89 (d, J = 1.8 Hz, 1H), 7.57 (dd, J = 8.3, 1.8 Hz, 1H), 5.21 (dd, J = 48.6, 4.0 Hz, 1H), 5.06 (dd, J = 17.3, 3.9 Hz, 1H); ¹⁹F NMR (471 MHz, CDCl₃) δ -108.71 (d, J = 1.4 Hz); ESIMS m/z244 ([M-H]^-)。 Example 5: Preparation of 2-bromo-4- (1-fluorovinyl) benzoic acid (C24)

In a 250 mL round bottom flask, methyl 2-bromo-4- (1-fluorovinyl) benzoate (C29) (1.8 g, 7.0 mmol), lithium hydroxide hydrate (0.88 g, 21 mmol), methanol. (7.0 mL), tetrahydrofuran (21 mL), and water (7.0 mL) were added and the reaction mixture was stirred at room temperature overnight. The mixture was concentrated, quenched with a pH 4 buffer and extracted with ethyl acetate to give the title compound as a white solid (1.0 g, 56%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.01. (d, J = 8.2 Hz, 1H), 7.89 (d, J = 1.8 Hz, 1H), 7.57 (dd, J = 8.3, 1.8 Hz, 1H), 5.21 (dd, J = 48.6, 4.0 Hz, 1H) , 5.06 (dd, J = 17.3, 3.9 Hz, 1H); ¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -108.71 (d, J = 1.4 Hz); ESIMS m / z244 ([MH] ^- ).

白色の固形物（１．９ｇ、９３％）として単離した：¹H NMR (400 MHz, メタノール-d₄) δ 7.95 (d, J = 1.5 Hz, 1H), 7.95 - 7.91 (m, 1H), 7.90 - 7.86 (m, 1H), 5.46 (dd, J = 50.0, 4.1 Hz, 1H), 5.09 (dd, J = 18.0, 4.1 Hz, 1H); ¹⁹F NMR (376 MHz, メタノール-d₄) δ -61.04 (d, J = 1.1 Hz),
-110.93；ESIMS m/z 233 ([M-H]^-)。 The following compounds were prepared in a manner similar to the procedure outlined in Example 5:
4- (1-Fluorovinyl) -2- (trifluoromethyl) benzoic acid (C25)

Isolated as a white solid (1.9 g, 93%): ¹ H NMR (400 MHz, methanol-d ₄ ) δ 7.95 (d, J = 1.5 Hz, 1H), 7.95 --7.91 (m, 1H) , 7.90 --7.76 (m, 1H), 5.46 (dd, J = 50.0, 4.1 Hz, 1H), 5.09 (dd, J = 18.0, 4.1 Hz, 1H); ¹⁹ F NMR (376 MHz, methanol-d ₄ ) δ -61.04 (d, J = 1.1 Hz),
-110.93; ESIMS m / z 233 ([MH] ^- ).

白色の固形物（３．５ｇ、７５％）として単離した：¹H NMR (400 MHz, アセトン-d₆) δ 7.97 (dd, J = 8.2, 0.9 Hz, 1H), 7.76 (d, J = 1.7 Hz, 1H), 7.70 (dd, J = 8.2, 1.7 Hz, 1H), 5.68 - 5.45 (m, 1H), 5.11 (dd, J = 18.2, 4.1 Hz, 1H); ¹⁹F NMR (376 MHz, アセトン-d₆) δ -108.71; ESIMS m/z 200 ([M-H]^-).
４−（１−フルオロビニル）−２−メチル安息香酸（Ｃ２７）

白色の固形物（０．５５０ｇ、８９％）として単離した：¹H NMR (400 MHz, メタノール-d₄) δ 7.92 (d, J = 8.1 Hz, 1H), 7.59 - 7.52 (m, 1H), 7.52 - 7.44 (m, 1H), 5.29 (dd, J = 50.1, 3.7 Hz, 1H), 4.93 (dd, J = 18.1, 3.7 Hz, 1H), 2.60 (s, 3H); ¹⁹F NMR (376 MHz, メタノール-d₄) δ -110.32 (d, J = 2.1 Hz); ESIMS m/z 181 ([M+H]⁺)。 2-Chloro-4- (1-fluorovinyl) benzoic acid (C26)

Isolated as white solid (3.5 g, 75%): ¹ H NMR (400 MHz, acetone-d ₆ ) δ 7.97 (dd, J = 8.2, 0.9 Hz, 1H), 7.76 (d, J = 1.7 Hz, 1H), 7.70 (dd, J = 8.2, 1.7 Hz, 1H), 5.68 --5.45 (m, 1H), 5.11 (dd, J = 18.2, 4.1 Hz, 1H); ¹⁹ F NMR (376 MHz, Acetone-d ₆ ) δ -108.71; ESIMS m / z 200 ([MH] ^- ).
4- (1-Fluorovinyl) -2-methylbenzoic acid (C27)

Isolated as white solid (0.550 g, 89%): ¹ H NMR (400 MHz, methanol-d ₄ ) δ 7.92 (d, J = 8.1 Hz, 1H), 7.59-7.52 (m, 1H) , 7.52 --7.44 (m, 1H), 5.29 (dd, J = 50.1, 3.7 Hz, 1H), 4.93 (dd, J = 18.1, 3.7 Hz, 1H), 2.60 (s, 3H); ¹⁹ F NMR (376) MHz, methanol-d ₄ ) δ -110.32 (d, J = 2.1 Hz); ESIMS m / z 181 ([M + H] ⁺ ).

１００ｍＬの丸底フラスコに、４−ブロモ−２−（トリフルオロメチル）安息香酸メチル（２．２５ｇ、８．００ｍｍｏｌ）、（１−フルオロビニル）（メチル）ジフェニルシラン（３．５８ｇ、１４．８ｍｍｏｌ）、及び１，３−ジメチルイミダゾリジン−２−オン（４０ｍＬ）を加えた。テトラキス（トリフェニルホスフィン）パラジウム（０）（０．４５９ｇ、０．４００ｍｍｏｌ）、ヨウ化銅（Ｉ）（０．０７６０ｍｇ、０．４００ｍｍｏｌ）、及びフッ化セシウム（３．６２ｇ、２３．９ｍｍｏｌ）を加えて、反応物を窒素雰囲気下、室温で２４時間撹拌した。混合物に水を加え、その混合物をヘキサン／ジエチルエーテルの３：１で希釈した。層を分離させ、有機層を硫酸ナトリウム上で乾燥させ、濃縮し、残渣をフラッシュカラムクロマトグラフィで精製して、表題化合物を無色の油状物（２．００ｇ、９６％）として得た：¹H NMR (400 MHz, CDCl₃) δ 7.96 - 7.87 (m, 1H), 7.83 (dq, J= 8.1, 0.7 Hz, 1H), 7.77 (dd, J= 8.2, 1.7 Hz, 1H), 5.23 (dd, J= 48.6, 4.0 Hz, 1H), 5.07 (dd, J= 17.4, 4.0 Hz, 1H), 3.95 (s, 3H); ¹⁹F NMR (376 MHz, CDCl3) δ -59.92, -108.73 (d, J = 1.4 Hz); EIMS m/z 248 ([M]⁺)。 Example 6: Preparation of 4- (1-fluorovinyl) -2- (trifluoromethyl) methyl benzoate (C28)

Methyl 4-bromo-2- (trifluoromethyl) benzoate (2.25 g, 8.00 mmol), (1-fluorovinyl) (methyl) diphenylsilane (3.58 g, 14.8 mmol) in a 100 mL round bottom flask. ), And 1,3-dimethylimidazolidine-2-one (40 mL) was added. Tetrakis (triphenylphosphine) palladium (0) (0.459 g, 0.400 mmol), copper (I) iodide (0.0760 mg, 0.400 mmol), and cesium fluoride (3.62 g, 23.9 mmol). In addition, the reaction was stirred at room temperature for 24 hours under a nitrogen atmosphere. Water was added to the mixture and the mixture was diluted 3: 1 with hexane / diethyl ether. The layers were separated, the organic layer was dried over sodium sulfate, concentrated and the residue was purified by flash column chromatography to give the title compound as a colorless oil (2.00 g, 96%): ¹ Hz NMR. (400 MHz, CDCl ₃ ) δ 7.96 --7.87 (m, 1H), 7.83 (dq, J = 8.1, 0.7 Hz, 1H), 7.77 (dd, J = 8.2, 1.7 Hz, 1H), 5.23 (dd, J = 48.6, 4.0 Hz, 1H), 5.07 (dd, J = 17.4, 4.0 Hz, 1H), 3.95 (s, 3H); ¹⁹ F NMR (376 MHz, CDCl3) δ -59.92, -108.73 (d, J = 1.4 Hz); EIMS m / z 248 ([M] ⁺ ).

無色の油状物（１．８ｇ、９３％）として単離した：¹H NMR (400 MHz, CDCl₃) δ 7.84 (d, J = 1.7 Hz, 1H), 7.82 (dd, J = 8.2, 0.9 Hz, 1H), 7.50 (d, J = 1.5 Hz, 1H), 5.16 (dd, J = 48.7, 3.9 Hz, 1H), 5.01 (dd, J = 17.3, 3.9 Hz, 1H), 3.94 (d, J = 2.2 Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ -108.61 (d, J = 1.5 Hz); ESIMS m/z258 ([M-H]^-)。 The following compounds were prepared in a manner similar to the procedure outlined in Example 6:
Methyl 2-bromo-4- (1-fluorovinyl) benzoate (C29)

Isolated as a colorless oil (1.8 g, 93%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.84 (d, J = 1.7 Hz, 1H), 7.82 (dd, J = 8.2, 0.9 Hz) , 1H), 7.50 (d, J = 1.5 Hz, 1H), 5.16 (dd, J = 48.7, 3.9 Hz, 1H), 5.01 (dd, J = 17.3, 3.9 Hz, 1H), 3.94 (d, J = 2.2 Hz, 3H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -108.61 (d, J = 1.5 Hz); ESIMS m / z258 ([MH] ^- ).

無色の油状物（２．１ｇ、９９％）として単離した：¹H NMR (400 MHz, CDCl₃) δ 7.86 (dd, J = 8.2, 0.9 Hz, 1H), 7.64 (d, J = 1.7 Hz, 1H), 7.48 (dd, J = 8.3, 1.8 Hz, 1H), 5.17 (dd, J = 48.7, 3.8 Hz, 1H), 5.02 (dd, J = 17.3, 3.9 Hz, 1H), 3.94 (s, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ -108.63 (d, J = 1.4 Hz); ESIMS m/z 214 ([M-H]^-)。 2-Chloro-4- (1-fluorovinyl) methyl benzoate (C30)

Isolated as a colorless oil (2.1 g, 99%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.86 (dd, J = 8.2, 0.9 Hz, 1H), 7.64 (d, J = 1.7 Hz) , 1H), 7.48 (dd, J = 8.3, 1.8 Hz, 1H), 5.17 (dd, J = 48.7, 3.8 Hz, 1H), 5.02 (dd, J = 17.3, 3.9 Hz, 1H), 3.94 (s, 3H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -108.63 (d, J = 1.4 Hz); ESIMS m / z 214 ([MH] ^- ).

無色の油状物（０．５ｇ、８５％）として単離した：¹H NMR (400 MHz, メタノール-d₄) δ 7.90 (d, J = 8.2 Hz, 1H), 7.51 (s, 1H), 7.49 (dd, J = 8.0, 1.6 Hz, 1H), 5.30 (dd, J = 50.1, 3.7 Hz, 1H), 4.95 (dd, J = 18.0, 3.7 Hz, 1H), 3.88 (d, J = 5.9 Hz, 3H), 2.59 (s, 3H); ¹⁹F NMR (376 MHz, メタノール-d₄) δ -110.41 (d, J = 1.3 Hz); ESIMS m/z 195 ([M+H]⁺)。 2-Chloro-4- (1-fluorovinyl) methyl benzoate (C31)

Isolated as a colorless oil (0.5 g, 85%): ¹ H NMR (400 MHz, methanol-d ₄ ) δ 7.90 (d, J = 8.2 Hz, 1H), 7.51 (s, 1H), 7.49 (dd, J = 8.0, 1.6 Hz, 1H), 5.30 (dd, J = 50.1, 3.7 Hz, 1H), 4.95 (dd, J = 18.0, 3.7 Hz, 1H), 3.88 (d, J = 5.9 Hz, 3H), 2.59 (s, 3H); ¹⁹ F NMR (376 MHz, methanol-d ₄ ) δ -110.41 (d, J = 1.3 Hz); ESIMS m / z 195 ([M + H] ⁺ ).

工程１：４−（２−ブロモ−１−フルオロエチル）−２−（トリフルオロメチル）安息香酸（Ｃ３２）２−（トリフルオロメチル）−４−ビニル安息香酸（５．３ｇ、２４ｍｍｏｌ）を、０℃でジクロロメタン（１２３ｍＬ）に溶解させ、トリエチルアミントリヒドロフルオライド（８．０ｍＬ、４９ｍｍｏｌ）に続いてＮ−ブロモスクシンイミド（８．７ｇ、４９ｍｍｏｌ）を加えた。反応混合物を室温まで加温しながら１６時間攪拌した。次に水を混合物に加え、ジクロロメタンで洗浄して、硫酸ナトリウム上で乾燥させ、ろ過し、濃縮して、黄色油状物（５．０ｇ、６５％）として表題化合物を得て、これをさらなる精製を行わずに使用した。 Example 7: Preparation of 4- (1-fluorovinyl) -2- (trifluoromethyl) benzoic acid (C25)

Step 1: 4- (2-Bromo-1-fluoroethyl) -2- (trifluoromethyl) benzoic acid (C32) 2- (trifluoromethyl) -4-vinylbenzoic acid (5.3 g, 24 mmol), It was dissolved in dichloromethane (123 mL) at 0 ° C., and triethylamine trihydrofluoride (8.0 mL, 49 mmol) was followed by N-bromosuccinimide (8.7 g, 49 mmol). The reaction mixture was stirred for 16 hours while warming to room temperature. Water is then added to the mixture, washed with dichloromethane, dried over sodium sulphate, filtered and concentrated to give the title compound as a yellow oil (5.0 g, 65%), which is further purified. Was used without doing.

Step 2: 4- (1-fluorovinyl) -2- (trifluoromethyl) benzoic acid (C25) 4- (2-bromo-1-fluoroethyl) -2- (trifluoromethyl) benzoic acid (4.3 g) , 14 mmol) was dissolved in methanol (68 mL) at 0 ° C., and potassium tert-butoxide (4.6 g, 41 mmol) was added as a solid with stirring. The reaction mixture was slowly warmed to 23 ° C. and then stirred for 4 hours. Hydrochloric acid (1N) was added slowly and the mixture was extracted with ethyl acetate. Purification by flash column chromatography using 0-40% acetone / hexanes gave the title compound as an off-white solid (1.7 g, 53%): ¹ H NMR (400 MHz, CDCl). ₃ ) δ 8.02 (d, J = 8.2 Hz, 1H), 8.00 --7.93 (m, 1H), 7.82 (dd, J = 8.2, 1.8 Hz, 1H), 5.27 (dd, J = 48.5, 4.1 Hz, 1H) ), 5.11 (dd, J = 17.3, 4.1 Hz, 1H).

白色の固形物（６．５ｇ、８６％）として単離した：¹H NMR (400 MHz、CDCl₃) δ 8.13 (d、J = 8.2 Hz、2H)、7.69 - 7.62 (m、2H)、5.21 (dd、J = 49.0、3.7 Hz、1H)、5.02 (dd、J = 17.5、3.7 Hz、1H); ¹⁹F NMR (376 MHz、CDCl₃) δ -108.35; ESIMS m/z 165 ([M-H]^-)。 The following compounds were prepared in a manner similar to the procedure outlined in Example 7.
4- (1-Fluorovinyl) Benzoic Acid (C33)

Isolated as white solid (6.5 g, 86%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.13 (d, J = 8.2 Hz, 2H), 7.69-7.62 (m, 2H), 5.21 (dd, J = 49.0, 3.7 Hz, 1H), 5.02 (dd, J = 17.5, 3.7 Hz, 1H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -108.35; ESIMS m / z 165 ([MH] ^- ).

無色の油状物（０．１６５ｇ、８９％）として単離した：¹H NMR (400 MHz, CDCl₃) δ 8.12 - 8.03 (m, 1H), 7.46 (dd, J= 5.8, 2.1 Hz, 2H), 5.17 (dd, J= 49.1, 3.7 Hz, 1H), 4.98 (dd, J= 17.5, 3.7 Hz, 1H), 2.68 (s, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ -108.50。 4- (1-Fluorovinyl) -2-methylbenzoic acid (C27)

Isolated as a colorless oil (0.165 g, 89%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.12-8.03 (m, 1H), 7.46 (dd, J = 5.8, 2.1 Hz, 2H) , 5.17 (dd, J = 49.1, 3.7 Hz, 1H), 4.98 (dd, J = 17.5, 3.7 Hz, 1H), 2.68 (s, 3H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -108.50.

Ｎ−ブロモスクシンイミド（１２．０ｇ、６７．５ｍｍｏｌ）を、２，２−ジフルオロ−１−（３，４，５−トリクロロフェニル）プロパン−１−オール（Ｃ４３）（６．００ｇ、２１．８ｍｍｏｌ）のジクロロメタン（７２．６ｍＬ）溶液に加えた。この撹拌溶液に、トリフェニルホスファイト（１７．１ｍＬ、６５．３ｍｍｏｌ）をゆっくりと滴下して加えると、反応混合物は暗褐色になった。次に反応混合物を３時間、還流で加熱した。溶媒を濃縮して、残渣をジエチルエーテルとともに研和した。固形物を濾過して、濾液を濃縮し、得られた油状物を、ヘキサン類を溶離液として使用したフラッシュカラムクロマトグラフィで精製することにより、表題化合物を無色透明の油状物（２．２０ｇ、２５％）として得た：¹H NMR (400 MHz, CDCl₃) δ 7.52 (s, 2H), 4.85 (dd, J = 12.3, 10.4 Hz, 1H), 1.77 (t, J= 18.2 Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ -92.14 - -95.01 (m); EIMS m/z 338 ([M]⁺)。 Example 8: Preparation of 5- (1-bromo-2,2-difluoropropyl) -1,2,3-trichlorobenzene (C34)

N-Bromosuccinimide (12.0 g, 67.5 mmol), 2,2-difluoro-1- (3,4,5-trichlorophenyl) propan-1-ol (C43) (6.00 g, 21.8 mmol) Was added to a solution of dichloromethane (72.6 mL). When triphenylphosphine (17.1 mL, 65.3 mmol) was slowly added dropwise to this stirred solution, the reaction mixture turned dark brown. The reaction mixture was then heated at reflux for 3 hours. The solvent was concentrated and the residue was triturated with diethyl ether. The solid was filtered, the filtrate was concentrated, and the resulting oil was purified by flash column chromatography using hexanes as the eluent to give the title compound a colorless and transparent oil (2.20 g, 25). %): ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.52 (s, 2H), 4.85 (dd, J = 12.3, 10.4 Hz, 1H), 1.77 (t, J = 18.2 Hz, 3H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -92.14 --- 95.01 (m); EIMS m / z 338 ([M] ⁺ ).

透明な油状物（２８ｇ、５６％）として単離した：¹H NMR (400 MHz, DMSO-d₆) δ 8.01 - 7.97 (m, 2H), 6.26 - 6.20 (m, 1H); IR (薄膜） 1168, 736, 557 cm^-1; ESIMS m/z 428 ([M+H]⁺)。 The following compounds were prepared in a manner similar to the procedure outlined in Example 8.
1,3-Dibromo-5- (1-bromo-2,2,2-trifluoroethyl) -2-chlorobenzene (C35)

Isolated as a clear oil (28 g, 56%): ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 8.01 --7.97 (m, 2H), 6.26 --6.20 (m, 1H); IR (thin film) 1168, 736, 557 cm ^-1 ; ESIMS m / z 428 ([M + H] ⁺ ).

透明な油状物（６．３２ｇ、８９％）として単離した：¹H NMR (300 MHz, DMSO-d₆) δ 7.39 (s, 2H), 6.17-6.09 (m, 1H), 2.35 (s, 6H); IR (薄膜) 1114, 754 cm^-1; ESIMS m/z 302 ([M+H]⁺)。 5- (1-Bromo-2,2,2-trifluoroethyl) -2-chloro-1,3-dimethylbenzene (C36)

Isolated as a clear oil (6.32 g, 89%): ¹ H NMR (300 MHz, DMSO-d ₆ ) δ 7.39 (s, 2H), 6.17-6.09 (m, 1H), 2.35 (s, 6H); IR (thin film) 1114, 754 cm ^-1 ; ESIMS m / z 302 ([M + H] ⁺ ).

透明な油状物（１９ｇ、４６％）として単離した：¹H NMR (400 MHz, CDCl₃) δ 7.54 - 7.51 (m, 2H), 5.03 - 4.98 (m, 1H); ¹⁹F NMR (376 MHz, CDCl₃) δ
-70.38。 2-Dibromo-5- (1-bromo-2,2,2-trifluoroethyl) -1,3-dichlorobenzene (C37)

Isolated as clear oil (19 g, 46%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.54 --7.51 (m, 2H), 5.03 --4.98 (m, 1H); ¹⁹ F NMR (376 MHz) , CDCl ₃ ) δ
-70.38.

無色の液体（１．４０ｇ、６５％）として単離した：¹H NMR (300 MHz, DMSO-d₆) δ 7.76 - 7.70 (m, 2H), 7.54 (dd, J = 8.4, 1.8 Hz, 1H), 5.81 - 5.73 (m, 1H), 1.67 (d, J = 18.9 Hz, 3H); IR (薄膜) 1118, 800, 499 cm^-1; EIMS m/z 304 ([M]⁺)。 4- (1-Bromo-2,2-difluoropropyl) -1,2-dichlorobenzene (C38)

Isolated as a colorless liquid (1.40 g, 65%): ¹ H NMR (300 MHz, DMSO-d ₆ ) δ 7.76 --7.70 (m, 2H), 7.54 (dd, J = 8.4, 1.8 Hz, 1H ), 5.81 --5.73 (m, 1H), 1.67 (d, J = 18.9 Hz, 3H); IR (thin film) 1118, 800, 499 cm ^-1 ; EIMS m / z 304 ([M] ⁺ ).

無色の液体（１０．５ｇ、５４％）として単離した：¹H NMR (400 MHz, CDCl₃) δ 7.76 (d, J = 1.2 Hz, 1H), 7.49 - 7.47 (m, 1H), 7.41 - 7.39 (m, 1H), 5.07 - 5.02 (m, 1H); IR (薄膜) 3437, 2924, 1631, 1114 cm^-1; EIMS m/z 350 ([M]⁺)。 2-Bromo-4- (1-bromo-2,2,2-trifluoroethyl) -1-chlorobenzene (C39)

Isolated as a colorless liquid (10.5 g, 54%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.76 (d, J = 1.2 Hz, 1H), 7.49 — 7.47 (m, 1H), 7.41 — 7.39 (m, 1H), 5.07 --5.02 (m, 1H); IR (thin film) 3437, 2924, 1631, 1114 cm ^-1 ; EIMS m / z 350 ([M] ⁺ ).

無色の油状物（８．０ｇ、７３％）として単離した：¹H NMR (300 MHz, CDCl₃) δ 7.59 - 7.57 (m, 1H), 7.42 - 7.33 (m, 1H), 7.20 -7.14 (m, 1H), 5.10 - 5.03 (m, 1H); IR (薄膜) 3429, 2926, 1502, 750 cm^-1; ESIMS m/z 292 ([M+H]⁺).
４−（１−ブロモ−２，２，２−トリフルオロエチル）−１−クロロ−２−フルオロベンゼン（Ｃ４１）

黄色の油状物（１．１ｇ、４５％）として単離した：¹H NMR (400 MHz、CDCl₃) δ 7.44 (dd、J = 8.3、7.5 Hz、1H)、7.34 (dd、J = 9.5、1.9 Hz、1H)、7.26 - 7.22 (m、1H)、5.08 (q、J = 7.1 Hz、1H); EIMS m/z291 ([M]⁺)。 4- (1-Bromo-2,2,2-trifluoroethyl) -2-chloro-1-fluorobenzene (C40)

Isolated as a colorless oil (8.0 g, 73%): ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.59 --7.57 (m, 1H), 7.42 --7.33 (m, 1H), 7.20 -7.14 ( m, 1H), 5.10 --5.03 (m, 1H); IR (thin film) 3429, 2926, 1502, 750 cm ^-1 ; ESIMS m / z 292 ([M + H] ⁺ ).
4- (1-Bromo-2,2,2-trifluoroethyl) -1-chloro-2-fluorobenzene (C41)

Isolated as a yellow oil (1.1 g, 45%): ^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 7.44 (dd, J = 8.3, 7.5 Hz, 1H), 7.34 (dd, J = 9.5, 1.9 Hz, 1H), 7.26 --7.22 (m, 1H), 5.08 (q, J = 7.1 Hz, 1H); EIMS m / z291 ([M] ⁺ ).

トリエチルアミン（２．４６ｍＬ、１７．６ｍｍｏｌ）及びメタンスルホニルクロリド（１．１０ｍＬ、１４．１ｍｍｏｌ）を、２，２−ジフルオロ−１−（３，４，５−トリクロロフェニル）ブタン−１−オール（Ｃ４４）（３．４０ｇ、１１．７ｍｍｏｌ）のジクロロメタン（５８．７ｍＬ）溶液に加えた。反応混合物を１時間撹拌し、その後ペンタンを加えた。濾過後、濾液を真空下で濃縮して、白色固形物を得た。固形物をジクロロメタン（５８．７ｍＬ）に溶解し、これに臭化鉄（ＩＩＩ）（６．９４ｇ、２３．５ｍｍｏｌ）を加えた。反応混合物を一晩攪拌した。混合物を水に注ぎ込み、ジクロロメタンで抽出した。有機層をブラインで洗浄して、硫酸ナトリウム上で乾燥させ、濾過及び濃縮した。ヘキサン類を溶離液として使用したフラッシュカラムクロマトグラフィで精製することにより、表題化合物を白色の固形物（３．５２ｇ、７２％）として得た：¹H NMR (400 MHz, CDCl₃) δ 7.51 (s, 2H), 4.85 (t, J = 12.1 Hz, 1H), 2.14 - 1.91 (m, 2H), 1.06 (t, J= 7.5 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 135.55, 134.39, 132.52, 129.48, 120.25 (t, J= 249.0 Hz), 49.76 (t, J = 30.3 Hz), 28.03 (t, J = 25.2 Hz), 6.06 (t, J = 5.1 Hz); ESIMS m/z 351 ([M-H]^-)。 Example 9: Preparation of 5- (1-bromo-2,2-difluorobutyl) -1,2,3-trichlorobenzene (C42)

Triethylamine (2.46 mL, 17.6 mmol) and methanesulfonyl chloride (1.10 mL, 14.1 mmol) with 2,2-difluoro-1- (3,4,5-trichlorophenyl) butane-1-ol (C44) ) (3.40 g, 11.7 mmol) was added to a solution of dichloromethane (58.7 mL). The reaction mixture was stirred for 1 hour and then pentane was added. After filtration, the filtrate was concentrated under vacuum to give a white solid. The solid was dissolved in dichloromethane (58.7 mL) and iron (III) bromide (6.94 g, 23.5 mmol) was added thereto. The reaction mixture was stirred overnight. The mixture was poured into water and extracted with dichloromethane. The organic layer was washed with brine, dried over sodium sulfate, filtered and concentrated. Purification by flash column chromatography using hexanes as eluent gave the title compound as a white solid (3.52 g, 72%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.51 (s). , 2H), 4.85 (t, J = 12.1 Hz, 1H), 2.14 --1.91 (m, 2H), 1.06 (t, J = 7.5 Hz, 3H); ¹³ C NMR (101 MHz, CDCl ₃ ) δ 135.55, 134.39, 132.52, 129.48, 120.25 (t, J = 249.0 Hz), 49.76 (t, J = 30.3 Hz), 28.03 (t, J = 25.2 Hz), 6.06 (t, J = 5.1 Hz); ESIMS m / z 351 ([MH] ^- ).

２，２−ジフルオロ−１−（３，４，５−トリクロロフェニル）プロパン−１−オン（Ｃ５２）（１．７５ｇ、６．４０ｍｍｏｌ）を室温でメタノール（６４．０ｍＬ）に溶解させ、水素化ホウ素ナトリウム（０．２９０ｇ、７．６８ｍｍｏｌ）を加えた。ガスの発生が終わるまで、反応物を室温で１時間攪拌した。反応混合物を水に注ぎ込み、ジエチルエーテルで抽出した。有機層をブラインで洗浄して、硫酸ナトリウム上で乾燥させ、濾過及び濃縮した。０％〜３０％のアセトン／ヘキサン類を溶離液として使用したフラッシュカラムクロマトグラフィで精製することにより、表題化合物を透明無色の油状物（１．６０ｇ、９１％）として得た：¹H NMR (400 MHz, CDCl₃) δ 7.50 (d, J = 0.9 Hz, 2H), 4.81 (td, J = 8.7, 3.8 Hz, 1H), 1.65 - 1.41 (m, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ -98.54 - -101.73 (m); IR (薄膜) 3405, 1555, 1389 cm^-1。 Example 10: Preparation of 2,2-difluoro-1- (3,4,5-trichlorophenyl) propane-1-ol (C43)

2,2-Difluoro-1- (3,4,5-trichlorophenyl) propan-1-one (C52) (1.75 g, 6.40 mmol) is dissolved in methanol (64.0 mL) at room temperature and borohydrided. Sodium borohydride (0.290 g, 7.68 mmol) was added. The reaction was stirred at room temperature for 1 hour until gas generation was complete. The reaction mixture was poured into water and extracted with diethyl ether. The organic layer was washed with brine, dried over sodium sulfate, filtered and concentrated. Purification by flash column chromatography using 0% to 30% acetone / hexanes as eluent gave the title compound as a clear colorless oil (1.60 g, 91%): ¹ H NMR (400). MHz, CDCl ₃ ) δ 7.50 (d, J = 0.9 Hz, 2H), 4.81 (td, J = 8.7, 3.8 Hz, 1H), 1.65 --1.41 (m, 3H); ¹⁹ F NMR (376 MHz, CDCl ₃₎ ) δ -98.54 --- 101.73 (m); IR (thin film) 3405, 1555, 1389 cm ^-1 .

透明無色の油状物（３．４ｇ、４８％）として単離した：¹H NMR (400 MHz, CDCl₃) δ 7.48 (d, J = 0.9 Hz, 2H), 4.87 - 4.70 (m, 1H), 2.54 (dt, J = 4.0, 1.0 Hz, 1H), 2.06 - 1.82 (m, 1H), 1.82 - 1.63 (m, 1H), 1.02 (t, J = 7.5 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 136.85, 134.20, 131.60, 127.54, 123.19 (t, J = 248.0 Hz), 73.71 (t, J = 30.0 Hz), 25.05 (t, J = 24.6 Hz), 5.35 (t, J = 5.2 Hz); EIMS m/z 287 ([M]⁺)。 The following compounds were prepared in a manner similar to the procedure outlined in Example 10:
2,2-Difluoro-1- (3,4,5-trichlorophenyl) butane-1-ol (C44)

Isolated as a clear, colorless oil (3.4 g, 48%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.48 (d, J = 0.9 Hz, 2H), 4.87-4.70 (m, 1H), 2.54 (dt, J = 4.0, 1.0 Hz, 1H), 2.06 --1.82 (m, 1H), 1.82 --1.63 (m, 1H), 1.02 (t, J = 7.5 Hz, 3H); ¹³ C NMR (101 MHz) , CDCl ₃ ) δ 136.85, 134.20, 131.60, 127.54, 123.19 (t, J = 248.0 Hz), 73.71 (t, J = 30.0 Hz), 25.05 (t, J = 24.6 Hz), 5.35 (t, J = 5.2) Hz); EIMS m / z 287 ([M] ⁺ ).

透明無色の油状物（２．７８ｇ、８９％）として単離した：¹H NMR (400 MHz, CDCl₃) δ 7.57 (dd, J = 2.0, 0.9 Hz, 1H), 7.46 (d, J = 8.3 Hz, 1H), 7.33 - 7.27 (m, 1H), 4.83 (td, J = 8.9, 3.7 Hz, 1H), 2.55 (dt, J = 3.8, 1.1 Hz, 1H), 1.50 (t, J = 18.9 Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ -99.52 (d, J = 249.6 Hz), -101.09 (d, J = 249.4 Hz); IR (薄膜) 3417 cm^-1。 1- (3,4-dichlorophenyl) -2,2-difluoropropane-1-ol (C45)

Isolated as a clear, colorless oil (2.78 g, 89%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.57 (dd, J = 2.0, 0.9 Hz, 1H), 7.46 (d, J = 8.3). Hz, 1H), 7.33 --7.27 (m, 1H), 4.83 (td, J = 8.9, 3.7 Hz, 1H), 2.55 (dt, J = 3.8, 1.1 Hz, 1H), 1.50 (t, J = 18.9 Hz) , 3H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -99.52 (d, J = 249.6 Hz), -101.09 (d, J = 249.4 Hz); IR (thin film) 3417 cm ^-1 .

トリメチル（トリフルオロメチル）シラン（１０．１ｍＬ、６８．４ｍｍｏｌ）及びフッ化テトラブチルアンモニウム（１．４４ｇ、４．５６ｍｍｏｌ）を、室温で３−ブロモ−４−クロロ−ベンズアルデヒド（１０．０ｇ、４５．６ｍｍｏｌ）のテトラヒドロフラン（１５０ｍＬ）撹拌溶液に加え、反応混合物を２時間撹拌した。反応混合物をジクロロメタンで希釈し、塩酸（２Ｎ）で洗浄した。分離した有機層をブラインで洗浄して、硫酸ナトリウム上で乾燥させ、濾過及び濃縮して、表題化合物を褐色の液体として得て、これをさらなる精製をせずに使用した（１３．２ｇ、９４％）：
¹H NMR (300 MHz, CDCl₃) δ 7.76 (s, 1H), 7.50 - 7.48 (m, 1H), 7.38 - 7.35 (m, 1H), 5.03 - 4.97 (m, 1H), 2.95 (br s, 1H); IR (薄膜) 3406, 2881, 1469, 814 cm^-1; EIMS m/z 288 ([M]⁺)。 Example 11: Preparation of 1- (3-Bromo-4-chlorophenyl) -2,2,2-trifluoroethanol (C46)

Tribromo-4-chloro-benzaldehyde (10.0 g, 45) of trimethyl (trifluoromethyl) silane (10.1 mL, 68.4 mmol) and tetrabutylammonium fluoride (1.44 g, 4.56 mmol) at room temperature. It was added to a .6 mmol) tetrahydrofuran (150 mL) stirring solution and the reaction mixture was stirred for 2 hours. The reaction mixture was diluted with dichloromethane and washed with hydrochloric acid (2N). The separated organic layer was washed with brine, dried over sodium sulphate, filtered and concentrated to give the title compound as a brown liquid which was used without further purification (13.2 g, 94). %):
^{1 1} H NMR (300 MHz, CDCl ₃ ) δ 7.76 (s, 1H), 7.50 --7.84 (m, 1H), 7.38 --7.35 (m, 1H), 5.03 --4.97 (m, 1H), 2.95 (br s, 1H); IR (thin film) 3406, 2881, 1469, 814 cm ^-1 ; EIMS m / z 288 ([M] ⁺ ).

淡黄色の液体（７．４ｇ、８５％）として単離した：¹H NMR (400 MHz, DMSO-d₆) δ 7.90 (s, 2H), 7.24 (d, J = 5.2 Hz, 1H), 5.33 (d, J = 6.4 Hz, 1H); IR (薄膜) 3370, 1175, 735, 541 cm^-1; EIMS m/z 366 ([M]⁺)。 The following compounds were prepared in a manner similar to the procedure outlined in Example 11.
1- (3,5-dibromo-4-chlorophenyl) -2,2,2-trifluoroethanol (C47)

Isolated as a pale yellow liquid (7.4 g, 85%): ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 7.90 (s, 2H), 7.24 (d, J = 5.2 Hz, 1H), 5.33 (d, J = 6.4 Hz, 1H); IR (thin film) 3370, 1175, 735, 541 cm ^-1 ; EIMS m / z 366 ([M] ⁺ ).

透明な液体（５．０ｇ、７０％）として単離した：¹H NMR (400 MHz, CDCl₃) δ 7.18 (s, 2H), 4.95 - 4.92 (m, 1H), 2.40 (s, 6H); IR (薄膜) 3378, 1124, 833 cm^-1; EIMS m/z238 ([M]⁺)。 1- (4-chloro-3,5-dimethylphenyl) -2,2,2-trifluoroethanol (C48)

Isolated as a clear liquid (5.0 g, 70%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.18 (s, 2H), 4.95-4.92 (m, 1H), 2.40 (s, 6H); IR (thin film) 3378, 1124, 833 cm ^-1 ; EIMS m / z 238 ([M] ⁺ ).

透明な油状物（３３ｇ、８６％）として単離した：¹H NMR (400 MHz, CDCl₃) δ 7.51 (s, 2H), 5.01 - 4.96 (m, 1H), 4.14 - 4.09 (m, 1H); ¹⁹F NMR (376 MHz, CDCl₃) δ -78.32。 1- (4-Bromo-3,5-dichlorophenyl) -2,2,2-trifluoroethanol (C49)

Isolated as a clear oil (33 g, 86%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.51 (s, 2H), 5.01 --4.96 (m, 1H), 4.14 --4.09 (m, 1H) ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -78.32.

透明な褐色のゴム状物（７．０ｇ、９７％）として単離した：¹H NMR (300 MHz, CDCl₃) δ 7.58 - 7.55 (m, 1H), 7.38 - 7.33 (m, 1H), 7.20 - 7.15 (m, 1H), 5.03 - 4.97 (m, 1H); EIMS m/z 228 ([M]⁺)。 1- (3-Chloro-4-fluorophenyl) -2,2,2-trifluoroethanol (C50)

Isolated as a clear brown rubbery material (7.0 g, 97%): ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.58 --7.55 (m, 1H), 7.38 --7.33 (m, 1H), 7.20 --7.15 (m, 1H), 5.03 --4.97 (m, 1H); EIMS m / z 228 ([M] ⁺ ).

透明無色の油状物（１．９７ｇ、７５％）として単離した：¹H NMR (400 MHz, CDCl₃) δ 7.52 - 7.37 (m, 1H), 7.32 (d, J= 9.6 Hz, 1H), 7.21 (d, J = 8.3 Hz, 1H), 5.03 (dd, J = 6.3, 3.6 Hz, 1H), 2.62 (d, J = 4.0 Hz, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 158.06 (J_CF = 188.9 Hz), 134.40 (d, J_CF = 6.6 Hz), 130.79, 123.83 (d, J_CF= 3.5 Hz), 122.4 (q, J_CF= 188.9 Hz), 115.8 (d, J = 25.3 Hz), 71.65 (q, J_CF = 31.6 Hz); EIMS m/z 228 ([M]⁺)。 1- (4-Chloro-3-fluorophenyl) -2,2,2-trifluoroethanol (C51)

Isolated as a clear, colorless oil (1.97 g, 75%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.52 --7.37 (m, 1H), 7.32 (d, J = 9.6 Hz, 1H), 7.21 (d, J = 8.3 Hz, 1H), 5.03 (dd, J = 6.3, 3.6 Hz, 1H), 2.62 (d, J = 4.0 Hz, 1H); ¹³ C NMR (101 MHz, CDCl ₃ ) δ 158.06 (J _CF = 188.9 Hz), 134.40 (d, J _CF = 6.6 Hz), 130.79, 123.83 (d, J _CF = 3.5 Hz), 122.4 (q, J _CF = 188.9 Hz), 115.8 (d, J = 25.3) Hz), 71.65 (q, J _CF = 31.6 Hz); EIMS m / z 228 ([M] ⁺ ).

窒素下、−７８℃で、ジエチルエーテル（３９．８ｍＬ）に溶解した５−ブロモ−１，２，３−トリクロロベンゼン（２．２８ｇ、８．７６ｍｍｏｌ）に、ｎ−ブチルリチウム（３．５０ｍＬ、８．７６ｍｍｏｌ）を加えた。溶液を３０分間撹拌した。これに、２，２−ジフルオロプロパン酸エチル（１．１０ｇ、７．９６ｍｍｏｌ、２０％ ｗ／ｗトルエン溶液として）を、１０分かけて滴下して加え、反応混合物をさらに１時間撹拌した。飽和塩化アンモニウム水溶液をこの混合物に加え、反応フラスコを室温まで加温しながら撹拌を続けた。次に反応混合物をジメチルエーテルで抽出し、水及びブラインで洗浄して、硫酸ナトリウム上で乾燥させ、濾過及び濃縮した。フラッシュカラムクロマトグラフィで精製することにより、表題化合物を淡黄色の油状物（１．７６ｇ、７３％）として得た：¹H NMR (400 MHz、CDCl₃) δ 8.11 (d、J = 0.9 Hz、2H)、1.89 (t、J = 19.6 Hz、3H); ¹⁹F NMR (376 MHz、CDCl₃) δ -92.66; ESIMS m/z 271 ([M-H]^-)。 Example 12: 2,2-difluoro-1- (3,4,5-trichlorophenyl)
Preparation of propane-1-one (C52)

N-Butyllithium (3.50 mL, 3.50 mL) in 5-bromo-1,2,3-trichlorobenzene (2.28 g, 8.76 mmol) dissolved in diethyl ether (39.8 mL) at −78 ° C. under nitrogen. 8.76 mmol) was added. The solution was stirred for 30 minutes. Ethyl 2,2-difluoropropanoate (1.10 g, 7.96 mmol, as a 20% w / w toluene solution) was added dropwise to this over 10 minutes, and the reaction mixture was stirred for an additional hour. Saturated aqueous ammonium chloride solution was added to the mixture and stirring was continued while warming the reaction flask to room temperature. The reaction mixture was then extracted with dimethyl ether, washed with water and brine, dried over sodium sulfate, filtered and concentrated. Purification by flash column chromatography gave the title compound as a pale yellow oil (1.76 g, 73%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.11 (d, J = 0.9 Hz, 2 H). ), 1.89 (t, J = 19.6 Hz, 3H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -92.66; ESIMS m / z 271 ([MH] ^- ).

油状物（２．３ｇ、６８％）として単離し、さらなる精製または特徴解析を行わずに使用した。 The following compounds were prepared in a manner similar to the procedure outlined in Example 12.
2,2-Difluoro-1- (3,4,5-trichlorophenyl) butane-1-one (C53)

It was isolated as an oil (2.3 g, 68%) and used without further purification or characterization.

無色の油状物（３．８９ｇ、７１％）として単離した：¹H NMR (400 MHz, CDCl₃) δ 8.21 - 8.18 (m, 1H), 7.99 - 7.93 (m, 1H), 7.59 (dd, J = 8.4, 4.2 Hz, 1H), 1.89 (t, J = 19.6 Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ -92.08 -
-93.21 (m); EIMS m/z238/240 ([M]⁺)。 1- (3,4-dichlorophenyl) -2,2-difluoropropane-1-one (C54)

Isolated as a colorless oil (3.89 g, 71%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.21 --8.18 (m, 1H), 7.99 --7.93 (m, 1H), 7.59 (dd, dd, J = 8.4, 4.2 Hz, 1H), 1.89 (t, J = 19.6 Hz, 3H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -92.08-
-93.21 (m); EIMS m / z 238/240 ([M] ⁺ ).

２５ｍＬのバイアルに、（Ｚ）−２−ブロモ−４−（１，４，４，４−テトラフルオロ−３−（３，４，５−トリクロロフェニル）ブタ−１−エン−１−イル）安息香酸（Ｃ１）（０．０６６ｇ、０．１３ｍｍｏｌ）、Ｎ−（２，２，２−トリフルオロエチル）ヒドラジンカルボキサミド塩酸塩（０．０３８ｇ、０．２０ｍｍｏｌ）、および（（１Ｈ−ベンゾ［ｄ］［１，２，３］トリアゾール−１−イル）オキシ）トリ（ピロリジン−１−イル）ホスホニウムヘキサフルオロリン酸塩（Ｖ）（０．１０ｇ、０．２０ｍｍｏｌ）のジクロロメタン（２．６ｍＬ）溶液を加え、橙色の懸濁液を得た。トリエチルアミン（０．０７３ｍＬ、０．５２ｍｍｏｌ）を加え、反応混合物を室温で一晩撹拌した。溶媒を濃縮し、残渣をフラッシュカラムクロマトグラフィで精製して、表題化合物を白色のゴム状物（０．０１３ｇ、１３％）として得た。 Example 13: (Z) -2- (2-bromo-4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) ) Preparation of benzoyl) -N- (2,2,2-trifluoroethyl) hydrazinecarboxamide (F2)

In a 25 mL vial, (Z) -2-bromo-4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) benzoic acid Acid (C1) (0.066 g, 0.13 mmol), N- (2,2,2-trifluoroethyl) hydrazine carboxamide hydrochloride (0.038 g, 0.20 mmol), and ((1H-benzo [d]). [1,2,3] Triazole-1-yl) oxy) Tri (pyrrolidin-1-yl) phosphonium hexafluorophosphate (V) (0.10 g, 0.20 mmol) in dichloromethane (2.6 mL). In addition, an orange suspension was obtained. Triethylamine (0.073 mL, 0.52 mmol) was added and the reaction mixture was stirred at room temperature overnight. The solvent was concentrated and the residue was purified by flash column chromatography to give the title compound as a white rubbery product (0.013 g, 13%).

黄色の油状物（０．０２ｇ、３０％）として単離した。 The following compounds were prepared in a manner similar to the procedure outlined in Example 13.
(Z) -2- (4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) -2- (trifluoromethyl) ) Benzoyl) -N- (2,2,2-trifluoroethyl) hydrazine carboxamide (F3)

It was isolated as a yellow oil (0.02 g, 30%).

黄色の油状物（０．１０１ｇ、７５％）として単離した。 (Z) -4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) porcine-1-ene-1-yl) -N'-(4,4,4) -Trifluorobutanoyl) -2- (trifluoromethyl) benzohydrazide (F4)

It was isolated as a yellow oil (0.101 g, 75%).

無色のゴム状物（０．０５５ｇ、３８％）として単離した。 (Z) -N'-methyl-4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) porcine-1-en-1-yl) -N'-( 4,4,4-trifluorobutanoyl) -2- (trifluoromethyl) benzohydrazide (F11)

It was isolated as a colorless rubbery substance (0.055 g, 38%).

無色のゴム状物（０．０２７ｇ、４２％）として単離した。 (Z) -2- (4- (1,4,4-trifluoro-3- (3,4,5-trichlorophenyl) penta-1-ene-1-yl) -2- (trifluoromethyl) benzoyl ) -N- (2,2,2-trifluoroethyl) hydrazine carboxamide (F12)

It was isolated as a colorless rubbery substance (0.027 g, 42%).

無色のゴム状物（０．０７２ｇ、６６％）として単離した。 (Z) -2-Chloro-4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) porcine-1-ene-1-yl) -N'-(4) , 4,4-Trifluorobutanoyl) Benzohydrazide (F20)

It was isolated as a colorless rubbery substance (0.072 g, 66%).

黄色のゴム状物（０．０７０ｇ、６７％）として単離した。 (Z) -2-iodo-4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) porcine-1-ene-1-yl) -N'-(4) , 4,4-Trifluorobutanoyl) benzohydrazide (F21)

It was isolated as a yellow rubbery substance (0.070 g, 67%).

黄色の油状物（０．１６０ｇ、７４％）として単離した：¹H NMR (400 MHz, CDCl₃) δ 8.28 (s, 1H), 7.61 - 7.54 (m, 1H), 7.49 - 7.35 (m, 4H), 5.74 (dd, J = 32.9, 9.6 Hz, 1H), 4.60 (p, J = 9.0 Hz, 1H), 3.23 (s, 3H), 2.50 (s, 3H), 1.47 (s, 9H); ¹⁹F NMR (376 MHz, CDCl₃) δ -69.47 (d, J = 2.1 Hz), -111.63; EISIMS m/z 567 ([M-H]^-)。 1-Methyl-2- (2-methyl-4- (1,4,5,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) benzoyl) hydrazine Carboxylic acid (Z) -tert-butyl (C55)

Isolated as a yellow oil (0.160 g, 74%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.28 (s, 1H), 7.61 --7.54 (m, 1H), 7.49 --7.35 (m,) 4H), 5.74 (dd, J = 32.9, 9.6 Hz, 1H), 4.60 (p, J = 9.0 Hz, 1H), 3.23 (s, 3H), 2.50 (s, 3H), 1.47 (s, 9H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -69.47 (d, J = 2.1 Hz), -111.63; EISIMS m / z 567 ([MH] ^- ).

白色のゴム状物（０．０８８ｇ、８７％）として単離した：¹H NMR (400 MHz, CDCl₃) δ 8.96 (s, 1H), 7.80 (d, J = 8.0 Hz, 2H), 7.42 (d, J = 6.4 Hz, 4H), 5.74 (d, J = 32.6 Hz, 1H), 4.59 (p, J = 8.6 Hz, 1H), 3.23 (d, J = 6.3 Hz, 3H), 1.48 (s, 9H); ¹⁹F NMR (376 MHz, CDCl₃) δ -69.42 (d, J = 5.9 Hz), -111.62 (d, J = 40.7 Hz); ESIMS m/z 555 ([M-H]^-)。 1-Methyl-2- (4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) benzoyl) hydrazinecarboxylic acid (Z) ) -Tert-Butyl (CC2)

Isolated as white rubber (0.088 g, 87%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.96 (s, 1H), 7.80 (d, J = 8.0 Hz, 2H), 7.42 ( d, J = 6.4 Hz, 4H), 5.74 (d, J = 32.6 Hz, 1H), 4.59 (p, J = 8.6 Hz, 1H), 3.23 (d, J = 6.3 Hz, 3H), 1.48 (s, 9H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -69.42 (d, J = 5.9 Hz), -111.62 (d, J = 40.7 Hz); ESIMS m / z 555 ([MH] ^- ).

ジイソプロピルエチルアミン（０．１８ｍＬ、１．０ｍｍｏｌ）、２−クロロ−１，３−ジメチル
イミダゾリジニウムヘキサフルオロリン酸塩（０．０９５ｇ、０．３４ｍｍｏｌ）、３Ｈ−［１，２，３］トリアゾロ［４，５−ｂ］ピリジン−３−オール（０．０４６ｇ、０．３４ｍｍｏｌ）、および４，４，４−トリフルオロブタンヒドラジド塩酸塩（０．０７２ｇ、０．３８ｍｍｏｌ）を、（Ｚ）−４−（３−（３，５−ジブロモ−４−クロロフェニル）−１，４，４，４−テトラフルオロブタ−１−エン−１−イル）−２−（トリフルオロメチル）安息香酸（Ｃ５）（０．２０ｇ、０．３４ｍｍｏｌ）のジクロロメタン（５ｍＬ）攪拌溶液に加え、反応混合物を室温で６時間攪拌した。反応混合物を水に注ぎ込み、ジクロロメタンで洗浄した。分離した有機層を水、ブラインで洗浄し、硫酸ナトリウム上で乾燥させ、濾過し、そして濃縮した。３０％の酢酸エチル／石油エーテルを溶離液として使用するフラッシュカラムクロマトグラフィで精製することにより、表題化合物を褐色の固形物（０．１１ｇ、３９％）として得た。 Example 14: (Z) -4- (3- (3,5-dibromo-4-chlorophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -N'-( Preparation of 4,4,4-trifluorobutanoyl) -2- (trifluoromethyl) benzohydrazide (F5)

Diisopropylethylamine (0.18 mL, 1.0 mmol), 2-chloro-1,3-dimethylimidazolidinium hexafluorophosphate (0.095 g, 0.34 mmol), 3H- [1,2,3] triazolo [ 4,5-b] Pyridine-3-ol (0.046 g, 0.34 mmol) and 4,4,5-trifluorobutanehydrazide hydrochloride (0.072 g, 0.38 mmol), (Z) -4. -(3- (3,5-dibromo-4-chlorophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoromethyl) benzoic acid (C5) ( 0.20 g, 0.34 mmol) was added to the stirred solution of dichloromethane (5 mL) and the reaction mixture was stirred at room temperature for 6 hours. The reaction mixture was poured into water and washed with dichloromethane. The separated organic layer was washed with water, brine, dried over sodium sulphate, filtered and concentrated. Purification by flash column chromatography using 30% ethyl acetate / petroleum ether as eluent gave the title compound as a brown solid (0.11 g, 39%).

淡黄色の固形物（０．１２０ｇ、４２％）として単離した。 The following compounds were prepared in a manner similar to the procedure outlined in Example 14.
(Z) -4- (3- (3,5-dichlorophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -N'-(4,4,5-trifluoro) Butanoyl) -2- (trifluoromethyl) benzohydrazide (F6)

It was isolated as a pale yellow solid (0.120 g, 42%).

淡黄色の固形物（０．１００ｇ、４１％）として単離した。 (Z) -4- (3- (3,4-dichlorophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -N'-(4,4,5-trifluoro) Butanoyl) -2- (trifluoromethyl) benzohydrazide (F7)

It was isolated as a pale yellow solid (0.100 g, 41%).

黄色のゴム状物（０．１１０ｇ、３８％）として単離した。 (Z) -2- (4- (3- (3,5-dichlorophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoromethyl) benzoyl) -1-Methyl-N'-(2,2,2-trifluoroethyl)
Hydrazine carboxamide (F8)

It was isolated as a yellow rubbery substance (0.110 g, 38%).

黄色の固形物（０．１４５ｇ、５８％）として単離した。 (Z) -4- (3- (3,5-dibromophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -N'-(4,4,5-tri Fluorobutanoyl) -2- (trifluoromethyl) benzohydrazide (F9)

It was isolated as a yellow solid (0.145 g, 58%).

黄色の固形物（０．１２０ｇ、４７％）として単離した。 (Z) -4- (3- (3,5-dichloro-4-fluorophenyl) -1,4,5,4-tetrafluorobuta-1-ene-1-yl) -N'-(4,4) , 4-Trifluorobutanoyl) -2- (trifluoromethyl) benzohydrazide (F10)

It was isolated as a yellow solid (0.120 g, 47%).

黄色のゴム状物（０．１１０ｇ、３７％）として単離した。 (Z) -2- (4- (3- (3,4-dichlorophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoromethyl) benzoyl) -1-Methyl-N- (2,2,2-trifluoroethyl) hydrazine carboxamide (F15)

It was isolated as a yellow rubbery substance (0.110 g, 37%).

黄色のゴム状物（０．１００ｇ、３３％）として単離した。 (Z) -2- (4- (3- (4-Chloro-3,5-dimethylphenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (tri) Fluoromethyl) benzoyl) -1-methyl-N- (2,2,2-trifluoroethyl) hydrazine carboxamide (F16)

It was isolated as a yellow rubbery substance (0.100 g, 33%).

オフホワイト色の固形物（０．１１０ｇ、４６％）として単離した。 (Z) -4- (3- (4-Bromo-3,5-dichlorophenyl) -1,4,5,4-tetrafluorobuta-1-ene-1-yl) -N'-(4,4) 4-Trifluorobutanoyl) -2- (trifluoromethyl) benzohydrazide (F27)

It was isolated as an off-white solid (0.110 g, 46%).

ジイソプロピルエチルアミン（０．１７ｍＬ、０．９８ｍｍｏｌ）、１−［ビス（ジメチルアミノ）メチレン］−１Ｈ−１，２，３−トリアゾロ［４，５−ｂ］ピリジニウム３−オキシドヘキサフルオロリン酸塩（０．１４ｇ、０．３６ｍｍｏｌ）、および１−アミノ−１−メチル−３−（２，２，２−トリフルオロエチル）尿素塩酸塩（０．０７４ｇ、０．３６ｍｍｏｌ）を、（Ｚ）−４−（３−（３，５−ジブロモフェニル）−１，４，４，４−テトラフルオロブタ−１−エン−１−イル）−２−（トリフルオロメチル）安息香酸（Ｃ８）（０．１８ｇ、０．３３ｍｍｏｌ）のジクロロメタン溶液に室温で加え、６時間攪拌した。次いで、反応混合物をジクロロメタンで希釈し、水で洗浄した。分離された有機層を硫酸ナトリウム上で乾燥させ、濾過及び濃縮した。２５％の酢酸エチル／石油エーテルを溶離液として使用したフラッシュカラムクロマトグラフィで精製することにより、表題化合物を淡黄色の固形物（０．１４ｇ、５１％）として得た。 Example 15: (Z) -2- (4- (3- (3,5-dibromophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (tri) Preparation of Fluoromethyl) Benzoyl) -1-Methyl-N- (2,2,2-Trifluoroethyl) Hydrazine Carboxamide (F14)

Diisopropylethylamine (0.17 mL, 0.98 mmol), 1- [bis (dimethylamino) methylene] -1H-1,2,3-triazolo [4,5-b] pyridinium 3-oxide hexafluorophosphate (0) .14 g, 0.36 mmol), and 1-amino-1-methyl-3- (2,2,2-trifluoroethyl) urea hydrochloride (0.074 g, 0.36 mmol), (Z) -4- (3- (3,5-dibromophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoromethyl) benzoic acid (C8) (0.18 g, It was added to a solution of 0.33 mmol) in dichloromethane at room temperature, and the mixture was stirred for 6 hours. The reaction mixture was then diluted with dichloromethane and washed with water. The separated organic layer was dried over sodium sulfate, filtered and concentrated. Purification by flash column chromatography using 25% ethyl acetate / petroleum ether as eluent gave the title compound as a pale yellow solid (0.14 g, 51%).

淡黄色のゴム状物（０．０６０ｇ、２５％）として単離した。 The following compounds were prepared in a manner similar to the procedure outlined in Example 15.
(Z) -2- (4- (3- (3,5-dichloro-4-vinylphenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (tri) Preparation of Fluoromethyl) Benzoyl) -1-Methyl-N- (2,2,2-Trifluoroethyl) Hydrazine Carboxamide (F17)

It was isolated as a pale yellow rubbery substance (0.060 g, 25%).

黄色の粘着性固形物（０．１０５ｇ、２８％）として単離した。 (Z) -2- (4- (3- (3,5-dibromo-4-chlorophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoro) Methyl) benzoyl) -1-methyl-N- (2,2,2-trifluoroethyl) hydrazine carboxamide (F18)

It was isolated as a yellow sticky solid (0.105 g, 28%).

黄色の固形物（０．１０５ｇ、４３％）として単離した。 (Z) -2- (4- (3- (3,5-dichloro-4-fluorophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (tri) Fluoromethyl) benzoyl) -1-methyl-N- (2,2,2-trifluoroethyl) hydrazine carboxamide (F22)

It was isolated as a yellow solid (0.105 g, 43%).

淡黄色のゴム状物（０．０７８ｇ、２０％）として単離した。 (Z) -2- (4- (3- (4-Bromo-3,5-dichlorophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoro) Methyl) benzoyl) -1-methyl-N- (2,2,2-trifluoroethyl) hydrazine carboxamide (F23)

It was isolated as a pale yellow rubbery substance (0.078 g, 20%).

オフホワイト色の固形物（０．０９５ｇ、３８％）として単離した。 (Z) -2- (4- (3- (3-Bromo-5-chlorophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoromethyl) Benzoyl) -1-methyl-N- (2,2,2-trifluoroethyl) hydrazine carboxamide (F25)

It was isolated as an off-white solid (0.095 g, 38%).

黄色のゴム状物（０．１４８ｇ、５７％）として単離した。 (Z) -2- (4- (3- (3,4-dibromophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoromethyl) benzoyl ) -1-Methyl-N- (2,2,2-trifluoroethyl) hydrazine carboxamide (F26)

It was isolated as a yellow rubbery substance (0.148 g, 57%).

工程１。（Ｚ）−Ｎ’−メチル−４−（１，４，４，４−テトラフルオロ−３−（３，４，５−トリクロロフェニル）ブタ−１−エン−１−イル）−２−（トリフルオロメチル）ベンゾヒドラジド塩酸塩：１００ｍＬの丸底フラスコに、１−メチル−２−（４−（１，４，４，４−テトラフルオロ−３−（３，４，５−トリクロロフェニル）ブタ−１−エン−１−イル）−２−（トリフルオロメチル）ベンゾイル）ヒドラジンカルボン酸（Ｚ）−ｔｅｒｔ−ブチル（Ｃ５９）（１．００ｇ、１．６０ｍｍｏｌ）、ジクロロメタン（１６ｍＬ）、および塩化水素（ジオキサン中、４Ｍ、０．４００ｍＬ、１．６０ｍｍｏｌ）を加え、黄色溶液を得た。この反応物を室温で６時間攪拌し、その後濃縮して黄色の泡状物を得て、これをさらに精製することなく、すなわち特徴解析を行うことなく使用した。 Example 16: (Z) -1-methyl-2- (4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) ) -2- (Trifluoromethyl) Benzoyl) -N- (2,2,2-trifluoroethyl) Hydrazine Carboxamide (F1) Preparation

Process 1. (Z) -N'-methyl-4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) -2- (tri) Fluoromethyl) benzohydrazide hydrochloride: 1-methyl-2- (4- (1,4,5,4-tetrafluoro-3- (3,4,5-trichlorophenyl) porcine-) in a 100 mL round bottom flask 1-ene-1-yl) -2- (trifluoromethyl) benzoyl) hydrazinecarboxylic acid (Z) -tert-butyl (C59) (1.00 g, 1.60 mmol), dichloromethane (16 mL), and hydrogen chloride (16 mL). 4M, 0.400 mL, 1.60 mmol) was added in dichloromethane to obtain a yellow solution. The reaction was stirred at room temperature for 6 hours and then concentrated to give a yellow foam, which was used without further purification, ie without feature analysis.

Step 2. (Z) -1-Methyl-2- (4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) -2- (Trifluoromethyl) Benzoyl) -N- (2,2,2-trifluoroethyl) Hydrazin Carboxamide: In a 25 mL vial, (Z) -N'-methyl-4- (1,4,4,4-tetra) Fluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) -2- (trifluoromethyl) benzohydrazide hydrochloride (0.150 g, 0.268 mmol), diisopropylethylamine (0) .140 mL, 0.803 mmol), and acetonitrile (2.7 mL) were added to give a yellow solution. 4-Nitrophenyl carbamic acid (2,2,2-trifluoroethyl) (0.106 g, 0.402 mmol) was added and the reaction was stirred at room temperature overnight. The reaction mixture was quenched with aqueous sodium bicarbonate solution, extracted with dichloromethane, concentrated and purified directly by reverse phase flash column chromatography to give the title compound as a yellow oil (0.0968 g, 52%). rice field.

２５ｍＬの丸底フラスコに、（Ｚ）−４−（１，４，４，４−テトラフルオロ−３−（３，４，５−トリクロロフェニル）ブタ−１−エン−１−イル）−２−（トリフルオロメチル）安息香酸（Ｃ２）（０．１２０ｇ、０．２４２ｍｍｏｌ）、塩化チオニル（０．０３１７ｇ、０．２６６ｍｍｏｌ）、および１，２−ジクロロエタン（５ｍＬ）を加えた。得られた混合物を２時間かん流で加熱し、室温まで冷却し、その後濃縮した。この残渣をジクロロメタンに溶解させ、４，４，４−トリフルオロ−Ｎ’−メチルブタンヒドラジド塩酸塩（０．０５５０ｇ、０．２６６ｍｍｏｌ）とトリエチルアミン（０．０５１５ｇ、０．５０８ｍｍｏｌ）を含有するジクロロメタン（５ｍＬ）溶液に、０℃で滴下して加えた。反応物を一晩室温で攪拌した。反応混合物をジクロロメタンで希釈し、希塩酸、重炭酸ナトリウム水溶液で洗浄し、硫酸マグネシウム上で乾燥させ、ろ過し、濃縮した。２％のアセトン／ジクロロメタンを溶離液として使用したフラッシュカラムクロマトグラフィで精製することにより、表題化合物を白色の泡状物（０．０８２０ｇ、５２％）として得た。 Example 17: (Z) -N-methyl-4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) porcine-1-ene-1-yl) -N Preparation of'-(4,4,4-trifluorobutanoyl) -2- (trifluoromethyl) benzohydrazide (F13)

In a 25 mL round bottom flask, (Z) -4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) -2- (Trifluoromethyl) benzoic acid (C2) (0.120 g, 0.242 mmol), thionyl chloride (0.0317 g, 0.266 mmol), and 1,2-dichloroethane (5 mL) were added. The resulting mixture was heated by perfusion for 2 hours, cooled to room temperature and then concentrated. This residue is dissolved in dichloromethane and contains dichloromethane (0.0515 g, 0.508 mmol) containing 4,4,4-trifluoro-N'-methylbutanehydrazide hydrochloride (0.0550 g, 0.266 mmol) and triethylamine (0.0515 g, 0.508 mmol). 5 mL) was added dropwise to the solution at 0 ° C. The reaction was stirred overnight at room temperature. The reaction mixture was diluted with dichloromethane, washed with dilute hydrochloric acid and aqueous sodium bicarbonate solution, dried over magnesium sulfate, filtered and concentrated. Purification by flash column chromatography using 2% acetone / dichloromethane as the eluent gave the title compound as a white foam (0.0820 g, 52%).

工程１。（Ｚ）−Ｎ’−メチル−４−（１，４，４，４−テトラフルオロ−３−（３，４，５−トリクロロフェニル）ブタ−１−エン−１−イル）−２−（トリフルオロメチル）ベンゾヒドラジド塩酸塩：１００ｍＬの丸底バイアルに、１−メチル−２−（４−（１，４，４，４−テトラフルオロ−３−（３，４，５−トリクロロフェニル）ブタ−１−エン−１−イル）−２−（トリフルオロメチル）ベンゾイル）ヒドラジンカルボン酸（Ｚ）−ｔｅｒｔ−ブチル（Ｃ６０）（１．００ｇ、１．６０ｍｍｏｌ）、ジクロロメタン（１６ｍＬ）、および塩化水素（ジオキサン中、４Ｍ、０．４００ｍＬ、１．６０ｍｍｏｌ）を加え、黄色溶液を得た。この反応物を室温で６時間攪拌し、その後濃縮して黄色の泡状物を得て、これをさらに精製することなく、すなわち特徴解析を行うことなく使用した。 Example 18: (Z) -3,3,3-trifluoro-N-methyl-N'-(4- (1,4,5,4-tetrafluoro-3- (3,4,5-trichlorophenyl) ) Preparation of porcine-1-en-1-yl) -2- (trifluoromethyl) benzoyl) propan-1-sulfonohydrazide (F19)

Process 1. (Z) -N'-methyl-4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) -2- (tri) Fluoromethyl) benzohydrazide hydrochloride: 1-methyl-2- (4- (1,4,5,4-tetrafluoro-3- (3,4,5-trichlorophenyl) porcine-) in a 100 mL round bottom vial 1-ene-1-yl) -2- (trifluoromethyl) benzoyl) hydrazinecarboxylic acid (Z) -tert-butyl (C60) (1.00 g, 1.60 mmol), dichloromethane (16 mL), and hydrogen chloride (16 mL). 4M, 0.400 mL, 1.60 mmol) was added in dichloromethane to obtain a yellow solution. The reaction was stirred at room temperature for 6 hours and then concentrated to give a yellow foam, which was used without further purification, ie without feature analysis.

Step 2. (Z) -3,3,3-trifluoro-N-methyl-N'-(4- (1,4,5,4-tetrafluoro-3- (3,4,5-trichlorophenyl) pig-1) -En-1-yl) -2- (trifluoromethyl) benzoyl) Propane-1-sulfonohydrazide (F19): In a 25 mL vial, (Z) -N'-methyl-4- (1,4,4) , 4-Tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-en-1-yl) -2- (trifluoromethyl) benzohydrazide hydrochloride (0.140 g, 0.250 mmol) 1,2-Dichloroethane ((3 mL)) was added, followed by 3,3,3-trifluoropropane-1-sulfonyl chloride (0.0350 mL, 0.275 mmol) and 4-methylmorpholin (0.0690 mL, 0. 625 mmol) was added and the reaction mixture was vortexed and then stirred for 48 hours. The mixture was filtered through a polytetrafluoroethylene syringe filter and the resulting liquid was concentrated under a stream of nitrogen gas. Purification by flash column chromatography. The title compound was obtained as a colorless glassy substance (0.033 g, 17%).

無色のガラス状物（０．０１４ｇ、１２％）として単離した。 The following compounds were prepared in a manner similar to the procedure outlined in Example 18:
(Z) -3,3,3-trifluoro-N'-(4- (1,4,5,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1) -Il) -2- (trifluoromethyl) benzoyl) Propane-1-sulfonohydrazide (F24)

It was isolated as a colorless glassy substance (0.014 g, 12%).

塩化水素（１，４−ジオキサン中、４Ｎ、５．０ｍＬ）を、Ｎ−（４，４，４−トリフルオロブタノイルアミノ）カルバミン酸ｔｅｒｔ−ブチル（Ｃ６４）（１．５ｇ、５．９ｍｍｏｌ）の１，４−ジオキサン（５ｍＬ）溶液に加え、２時間室温で攪拌した。反応混合物を濃縮し、得られた残渣をペンタンで洗浄、ろ過し、真空下で乾燥させて、オフホワイト色の固形物（１．０ｇ、７４％）として表題化合物を得た：融点１８７〜１９０℃；¹H NMR (400 MHz, DMSO-d₆) δ 11.03 (br s, 1H), 10.60 - 10.41 (m, 3H), 2.56 - 2.45 (m, 4H); ESIMS m/z156 ([M-HCl]⁺)。 Example 19: Preparation of 4,4,4-trifluorobutane hydrazide hydrochloride (C55)

Hydrogen chloride (4N, 5.0 mL in 1,4-dioxane), tert-butyl N- (4,4,4-trifluorobutanoylamino) carbamic acid (C64) (1.5 g, 5.9 mmol) Was added to a solution of 1,4-dioxane (5 mL) and stirred at room temperature for 2 hours. The reaction mixture was concentrated and the resulting residue was washed with pentan, filtered and dried under vacuum to give the title compound as an off-white solid (1.0 g, 74%): melting point 187-190. ℃; ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 11.03 (br s, 1H), 10.60 --- 10.41 (m, 3H), 2.56 --2.45 (m, 4H); ESIMS m / z156 ([M-HCl) ] ⁺ ).

４−メチルモルホリン（１．６ｇ、１６ｍｍｏｌ）を、４，４，４−トリフルオロブタン酸（１．５ｇ、１１ｍｍｏｌ）のジクロロメタン（２０ｍＬ）溶液に−７８℃で加え、５分間攪拌した。カルボノクロリデートイソブチル（１．７ｇ、１３ｍｍｏｌ）をこの混合物に加え、さらに１０分間攪拌した。Ｎ−アミノカルバミン酸ｔｅｒｔ−ブチル（１．７ｇ、１３ｍｍｏｌ）を加え、反応物を２時間室温まで加温した。反応混合物をジクロロメタンで希釈し、水で洗浄して、硫酸ナトリウム上で乾燥させ、濾過し、そして濃縮した。３０％酢酸エチル／石油エーテルを溶離液として使用するフラッシュカラムクロマトグラフィーで精製し、オフホワイト色の固形物（１．５ｇ、５２％）として表題化合物を得た：融点９５〜９８℃；¹H NMR (400 MHz, CDCl₃) δ 7.19 (br s, 1H), 6.42 (s, 1H), 2.60 - 2.48 (m, 4H), 1.49 (s, 9H); ESIMS m/z 156 ([M-tert ブチル CO]⁺)。 Example 20: Preparation of tert-butyl 2- (4,4,4-trifluorobutanoyl) hydrazine carboxylic acid (C56)

4-Methylmorpholine (1.6 g, 16 mmol) was added to a solution of 4,4,4-trifluorobutanoic acid (1.5 g, 11 mmol) in dichloromethane (20 mL) at −78 ° C. and stirred for 5 minutes. Carbonochloridate isobutyl (1.7 g, 13 mmol) was added to the mixture and stirred for an additional 10 minutes. Tert-Butyl N-aminocarbamic acid (1.7 g, 13 mmol) was added and the reaction was warmed to room temperature for 2 hours. The reaction mixture was diluted with dichloromethane, washed with water, dried over sodium sulfate, filtered and concentrated. Purification by flash column chromatography using 30% ethyl acetate / petroleum ether as eluent gave the title compound as an off-white solid (1.5 g, 52%): melting point 95-98 ° C; ¹ H. NMR (400 MHz, CDCl ₃ ) δ 7.19 (br s, 1H), 6.42 (s, 1H), 2.60-2.48 (m, 4H), 1.49 (s, 9H); ESIMS m / z 156 ([M-tert Butyl CO] ⁺ ).

２５ｍＬのバイアルに、２−（４−（１，４，４，４−テトラフルオロ−３−（３，４，５−トリクロロフェニル）ブタ−１−エン−１−イル）−２−（トリフルオロメチル）ベンゾイル）ヒドラジンカルボン酸（Ｚ）−ｔｅｒｔ−ブチル（Ｃ６１）（０．３１７ｇ、０．５２０ｍｍｏｌ）と塩化水素（ジオキサン中、４Ｍ、５．００ｍＬ、２０．０ｍｍｏｌ）を加え、黄色溶液を得た。この溶液を、ＬＣＭＳが脱保護が完了したことを示すまで攪拌した。反応物を濃縮して、表題化合物を固形物として得た（０．２８０ｇ、９９％）：¹H NMR (400 MHz, DMSO-d₆) δ 11.69 (s, 1H), 8.22 (d, J = 1.7 Hz, 1H), 8.12 (dd, J = 8.0, 1.7 Hz, 1H), 8.06 (s, 2H), 7.74 (d, J = 8.1 Hz, 1H), 6.87 (dd, J = 35.7, 10.1 Hz, 1H), 5.26 (p, J = 9.4 Hz, 1H); ESIMS m/z 511 ([M+H]⁺)。 Example 21: Preparation of 2- (4,4,4-trifluorobutanoyl) hydrazine carboxylate tert-butyl (C57)

2- (4- (1,4,5,4-Tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) -2- (trifluoro) in a 25 mL vial Methyl) benzoyl) hydrazinecarboxylic acid (Z) -tert-butyl (C61) (0.317 g, 0.520 mmol) and hydrogen chloride (4M, 5.00 mL, 20.0 mmol in dioxane) were added to obtain a yellow solution. rice field. The solution was stirred until LCMS showed that deprotection was complete. The reaction was concentrated to give the title compound as a solid (0.280 g, 99%): ^{1 1} H NMR (400 MHz, DMSO-d ₆ ) δ 11.69 (s, 1H), 8.22 (d, J = 1.7 Hz, 1H), 8.12 (dd, J = 8.0, 1.7 Hz, 1H), 8.06 (s, 2H), 7.74 (d, J = 8.1 Hz, 1H), 6.87 (dd, J = 35.7, 10.1 Hz, 1H), 5.26 (p, J = 9.4 Hz, 1H); ESIMS m / z 511 ([M + H] ⁺ ).

２５ｍＬのバイアルに、（Ｚ）−２−クロロ−４−（１，４，４，４−テトラフルオロ−３−（３，４，５−トリクロロフェニル）ブタ−１−エン−１−イル）安息香酸（Ｃ４）（０．２９０ｇ、０．６２８ｍｍｏｌ）、１−メチルヒドラジンカルボン酸塩酸塩ｔｅｒｔ−ブチル（０．１７２ｇ、０．９４１ｍｍｏｌ）、（（１Ｈ−ベンゾ［ｄ］［１，２，３］トリアゾール−１−イル）オキシ）トリ（ピロリジン−１−イル）ホスホニウムヘキサフルオロリン酸塩（Ｖ）（０．４９０ｇ、０．９４１ｍｍｏｌ）、およびジクロロメタン（６．３ｍＬ）を加え、橙色の懸濁液を得た。トリエチルアミン（０．３５０ｍＬ、２．５１ｍｍｏｌ）を加え、反応混合物を室温で一晩撹拌した。溶媒を濃縮し、残渣をフラッシュカラムクロマトグラフィで精製して、表題化合物を無色の油状物（０．３６１ｇ、８８％）として得た：¹H NMR (400 MHz, CDCl₃) δ 8.55 (s, 1H), 7.60 (d, J = 1.6 Hz, 1H), 7.56 - 7.46 (m, 1H), 7.44 (s, 2H), 5.81 (dd, J = 32.6, 9.6 Hz, 1H), 4.60 (p, J = 8.9 Hz, 1H), 3.23 (s, 3H), 1.48 (s, 9H); ¹⁹F NMR (376 MHz, CDCl₃) δ -69.39, -112.07; ESIMS m/z 589 ([M-H]^-)。 Example 22: 2- (2-Chloro-4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) benzoyl)- Preparation of 1-Methylhydrazine Carboxylic Acid (Z) -tert-Butyl (C58)

In a 25 mL vial, (Z) -2-chloro-4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) benzoic acid Acid (C4) (0.290 g, 0.628 mmol), 1-methylhydrazine carboxylate tert-butyl (0.172 g, 0.941 mmol), ((1H-benzo [d] [1,2,3]) Triazole-1-yl) oxy) tri (pyrrolidin-1-yl) phosphonium hexafluorophosphate (V) (0.490 g, 0.941 mmol) and dichloromethane (6.3 mL) were added, and an orange suspension was added. Got Triethylamine (0.350 mL, 2.51 mmol) was added and the reaction mixture was stirred at room temperature overnight. The solvent was concentrated and the residue was purified by flash column chromatography to give the title compound as a colorless oil (0.361 g, 88%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.55 (s, 1 H). ), 7.60 (d, J = 1.6 Hz, 1H), 7.56 --7.46 (m, 1H), 7.44 (s, 2H), 5.81 (dd, J = 32.6, 9.6 Hz, 1H), 4.60 (p, J = 8.9 Hz, 1H), 3.23 (s, 3H), 1.48 (s, 9H); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -69.39, -112.07; ESIMS m / z 589 ([MH] ^- ).

黄色の油状物（０．０６０ｇ、５５％）として単離した：¹H NMR (400 MHz, CDCl₃) δ 7.88 (s, 1H), 7.79 (d, J = 7.8 Hz, 1H), 7.67 (s, 1H), 7.44 (s, 2H), 5.85 (dd, J = 32.5, 9.6 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), 3.23 (s, 3H), 1.50 (s, 9H); ¹⁹F NMR (376 MHz, CDCl₃) δ -59.13, -69.31 (d, J = 2.3 Hz), -111.99 (d, J= 37.0 Hz); ESIMS m/z 623 ([M-H]^-)。 The following compounds were prepared in a manner similar to the procedure outlined in Example 22:
1-Methyl-2- (4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) -2- (trifluoromethyl) ) Benzoyl) Hydrazine carboxylic acid (Z) -tert-butyl (C59)

Isolated as a yellow oil (0.060 g, 55%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.88 (s, 1H), 7.79 (d, J = 7.8 Hz, 1H), 7.67 (s) , 1H), 7.44 (s, 2H), 5.85 (dd, J = 32.5, 9.6 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), 3.23 (s, 3H), 1.50 (s, 9H) ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -59.13, -69.31 (d, J = 2.3 Hz), -111.99 (d, J = 37.0 Hz); ESIMS m / z 623 ([MH] ^- ).

２５ｍＬのバイアルに、（Ｚ）−４−（１，４，４，４−テトラフルオロ−３−（３，４，５−トリクロロフェニル）ブタ−１−エン−１−イル）−２−（トリフルオロメチル）塩化ベンゾイル（Ｃ２２）（０．４９０ｇ、０．９５３ｍｍｏｌ）のジオキサン（１０ｍＬ）溶液を加え、橙色の溶液を得た。ヒドラジンカルボン酸ｔｅｒｔ−ブチル（０．５０４ｇ、３．８１ｍｍｏｌ）を加え、反応混合物を掻き混ぜることにより攪拌した。ＬＣＭＳ解析により反応が完了したと判断されたとき、溶媒を濃縮した。得られた橙色の油状物を酢酸エチルに溶解させ、クエン酸水溶液（５％）、水、ブラインで洗浄し、硫酸マグネシウム上で乾燥させ、ろ過し、そして濃縮した。０〜１００％酢酸エチル／ヘキサン類を溶離液として使用するフラッシュカラムクロマトグラフィで精製し、次いで得られた固形物を４０℃の真空オーブン中で３時間乾燥させることにより、表題化合物を黄色の固形物（０．５７１ｇ、８８％）として得た：¹H NMR (500 MHz, CDCl₃) δ 7.90 - 7.87 (m, 1H), 7.79 (dd, J= 8.1, 1.7 Hz, 1H), 7.76 - 7.71 (m, 1H), 7.56 (s, 1H), 7.44 (s, 2H), 6.70 (s, 1H), 5.85 (dd, J = 32.5, 9.6 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), 1.50 (s, 9H); ¹⁹F NMR (471 MHz, CDCl₃) δ -59.26 , -69.29 (d, J = 8.8 Hz), -112.01 (d, J = 32.4 Hz); IR (薄膜) 3283, 2983, 1737, 1681 cm^-1。 Example 23: 2- (4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) -2- (trifluoromethyl) ) Benzoyl) Preparation of hydrazinecarboxylic acid (Z) -tert-butyl (C60)

In a 25 mL vial, (Z) -4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) -2- (tri) A solution of fluoromethyl) benzoyl chloride (C22) (0.490 g, 0.953 mmol) in dioxane (10 mL) was added to give an orange solution. Tert-Butyl hydrazine carboxylic acid (0.504 g, 3.81 mmol) was added and the reaction mixture was stirred by stirring. When the reaction was determined to be complete by LCMS analysis, the solvent was concentrated. The orange oil obtained was dissolved in ethyl acetate, washed with aqueous citric acid solution (5%), water and brine, dried over magnesium sulfate, filtered and concentrated. Purification by flash column chromatography using 0-100% ethyl acetate / hexanes as eluent, followed by drying the resulting solid in a vacuum oven at 40 ° C. for 3 hours to give the title compound a yellow solid. Obtained as (0.571 g, 88%): ^{1 1 1} H NMR (500 MHz, CDCl ₃ ) δ 7.90 --7.77 (m, 1H), 7.79 (dd, J = 8.1, 1.7 Hz, 1H), 7.76 --7.71 ( m, 1H), 7.56 (s, 1H), 7.44 (s, 2H), 6.70 (s, 1H), 5.85 (dd, J = 32.5, 9.6 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H ), 1.50 (s, 9H); ¹⁹ F NMR (471 MHz, CDCl ₃ ) δ -59.26, -69.29 (d, J = 8.8 Hz), -112.01 (d, J = 32.4 Hz); IR (thin film) 3283 , 2983, 1737, 1681 cm ^-1 .

１００ｍＬの丸底フラスコに、１−メチルヒドラジンカルボン酸ｔｅｒｔ−ブチル（０．３０１ｇ、２．０６ｍｍｏｌ）、トリエチルアミン（０．２１７ｇ、２．１５ｍｍｏｌ）、およびジクロロメタン（１５ｍＬ）を加え、無色溶液を得た。反応物を０℃に冷却し、４，４，４−トリフルオロブタノイルクロリド（０．３００ｇ、１．８７ｍｍｏｌ）のジクロロメタン（５ｍＬ）溶液を１時間かけて加えた。反応物を、さらに１時間、０℃で攪拌させて、次いで室温で１５時間攪拌した。反応混合物を分液漏斗に移し、炭酸ナトリウム水溶液、水およびブラインで洗浄し、硫酸マグネシウム上で乾燥させ、ろ過し、濃縮して、黄色の液体として表題化合物（０．４９０ｇ、９７％）を得た：¹H NMR (400 MHz, CDCl₃) δ 7.27 (s, 1H), 3.14 (d, J = 10.6 Hz, 3H), 2.50 (dddd, J = 23.7, 17.4, 9.2, 5.4 Hz, 4H), 1.47 (m, 9H)。 Example 24: Preparation of 1-methyl-2- (4,4,4-trifluorobutanoyl) hydrazine carboxylic acid tert-butyl (C62)

To a 100 mL round bottom flask, tert-butyl 1-methylhydrazine carboxylic acid (0.301 g, 2.06 mmol), triethylamine (0.217 g, 2.15 mmol), and dichloromethane (15 mL) were added to obtain a colorless solution. .. The reaction was cooled to 0 ° C. and a solution of 4,4,4-trifluorobutanoyl chloride (0.300 g, 1.87 mmol) in dichloromethane (5 mL) was added over 1 hour. The reaction was stirred for an additional hour at 0 ° C. and then at room temperature for 15 hours. The reaction mixture is transferred to a separatory funnel, washed with aqueous sodium carbonate solution, water and brine, dried over magnesium sulphate, filtered and concentrated to give the title compound (0.490 g, 97%) as a yellow liquid. T: ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.27 (s, 1H), 3.14 (d, J = 10.6 Hz, 3H), 2.50 (dddd, J = 23.7, 17.4, 9.2, 5.4 Hz, 4H), 1.47 (m, 9H).

塩化水素（１，４−ジオキサン中、４Ｎ、５．０ｍＬ）を、Ｎ−（４，４，４−トリフルオロブタノイルアミノ）カルバミン酸ｔｅｒｔ−ブチル（Ｃ６２）（０．４９０ｇ、１．８１３ｍｍｏｌ）の１，４−ジオキサン（５ｍＬ）溶液に加え、２時間室温で攪拌した。反応物を濃縮し、残渣をペンタンで洗浄、ろ過し、真空下で乾燥させて、オフホワイト色の固形物（０．３５０ｇ、９３％）として表題化合物を得た：融点１６７〜１７０℃；¹H NMR (400 MHz, DMSO-d₆) δ 11.20 (s, 1H), 10.80 - 10.30 (br s, 3H), 2.70 - 2.53 (m, 4H); ¹⁹F NMR (376 MHz, DMSO-d₆) δ -65.19; ESIMS m/z 170 ([M-HCl]⁺)。 Example 25: Preparation of 4,4,4-trifluoro-N'-methylbutanehydrazide hydrochloride (C63)

Hydrogen chloride (4N, 5.0 mL in 1,4-dioxane), tert-butyl N- (4,4,4-trifluorobutanoylamino) carbamic acid (C62) (0.490 g, 1.813 mmol) Was added to a solution of 1,4-dioxane (5 mL) and stirred at room temperature for 2 hours. The reaction was concentrated, the residue was washed with Pentan, filtered and dried under vacuum to give the title compound as an off-white solid (0.350 g, 93%): melting point 167-170 ° C; ¹ 1 F NMR (400 MHz, DMSO-d ₆ ) δ 11.20 (s, 1H), 10.80 --10.30 (br s, 3H), 2.70 --2.53 (m, 4H); ¹⁹ F NMR (376 MHz, DMSO-d ₆ ) δ -65.19; ESIMS m / z 170 ([M-HCl] ⁺ ).

５００ｍＬの丸底フラスコに、メチルヒドラジン（７．８１ｇ、１６９ｍｍｏｌ）とジクロロメタン（１５０ｍＬ）を加え、無色溶液を得た。反応管を０℃に冷却し、４，４，４−トリフルオロブタノイルクロリド（２．７２ｇ、１６．９ｍｍｏｌ）のジクロロメタン（５０ｍＬ）溶液を２時間かけて加えた。反応混合物をさらに１時間、０℃で攪拌し、次いで室温で１５時間攪拌した。反応混合物を分液漏斗に移し、炭酸ナトリウム水溶液、水およびブラインで洗浄し、硫酸マグネシウム上で乾燥させ、ろ過し、濃縮して、黄色の液体として表題化合物（２．９１ｇ、９１％）を得た：¹H NMR (400 MHz, CDCl₃) δ 3.77 (s, 2H), 3.20 (s, 3H), 2.95 - 2.84 (m, 2H), 2.51 - 2.34 (m, 2H); ¹³C NMR (101 MHz, CDCl₃) δ 172.82 , 127.22 (q, J_CF = 276.0 Hz), 38.72 , 29.54 (q, J_CF = 29.3 Hz), 25.69 (q, J_CF = 3.1 Hz); ¹⁹F NMR (376 MHz, CDCl₃) δ -66.70。 Example 26: Preparation of 4,4,4-trifluoro-N-methylbutanehydrazide (C64)

Methylhydrazine (7.81 g, 169 mmol) and dichloromethane (150 mL) were added to a 500 mL round bottom flask to obtain a colorless solution. The reaction tube was cooled to 0 ° C. and a solution of 4,4,4-trifluorobutanoyl chloride (2.72 g, 16.9 mmol) in dichloromethane (50 mL) was added over 2 hours. The reaction mixture was stirred for an additional hour at 0 ° C. and then at room temperature for 15 hours. The reaction mixture was transferred to a liquid separator, washed with aqueous sodium carbonate, water and brine, dried over magnesium sulfate, filtered and concentrated to give the title compound (2.91 g, 91%) as a yellow liquid. T: ¹ H NMR (400 MHz, CDCl ₃ ) δ 3.77 (s, 2H), 3.20 (s, 3H), 2.95 --2.84 (m, 2H), 2.51 --2.34 (m, 2H); ¹³ C NMR (101) MHz, CDCl ₃ ) δ 172.82, 127.22 (q, J _CF = 276.0 Hz), 38.72, 29.54 (q, J _CF = 29.3 Hz), 25.69 (q, J _CF = 3.1 Hz); ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -66.70.

２５０ｍＬの丸底フラスコに、１−メチルヒドラジンカルボン酸ｔｅｒｔ−ブチル（５．００ｇ、３４．２ｍｍｏｌ）とジクロロメタン（１００ｍＬ）を加え、無色溶液を得た。この反応混合物に、水酸化ナトリウム（１．０Ｍ，３３．０ｍＬ）、次いでベンジルカルボノクロリデート（５．８４ｇ、３４．２ｍｍｏｌ）を加え、室温で２時間攪拌した。反応混合物を分液漏斗に移し、炭酸ナトリウム水溶液、水およびブラインで洗浄し、硫酸マグネシウム上で乾燥させ、ろ過し、そして濃縮した。フラッシュカラムクロマトグラフィーで精製し、白色の固形物として表題化合物（８．５０ｇ、８１％）を得た：融点７１〜７３℃；¹H NMR (400 MHz, CDCl₃) δ 7.47 - 7.32 (m, 5H), 6.54 (br s, 1H), 5.17 (s, 2H), 3.14 (s, 3H), 1.42 (s, 9H); IR (薄膜) 3294, 2977, 1704, 1366, 1152 cm^-1; ESIMS m/z 279 ([M-H]^-)。 Example 27: Preparation of 2-benzyl1-tert-butyl (C65) 1-methylhydrazine-1,2-dicarboxylic acid

To a 250 mL round bottom flask, tert-butyl 1-methylhydrazine carboxylic acid (5.00 g, 34.2 mmol) and dichloromethane (100 mL) were added to obtain a colorless solution. Sodium hydroxide (1.0 M, 33.0 mL) and then benzyl carbonate chloride (5.84 g, 34.2 mmol) were added to the reaction mixture, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was transferred to a separatory funnel, washed with aqueous sodium carbonate solution, water and brine, dried over magnesium sulphate, filtered and concentrated. Purification by flash column chromatography gave the title compound (8.50 g, 81%) as a white solid: melting point 71-73 ° C; ^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 7.47-7.32 (m, m, 5H), 6.54 (br s, 1H), 5.17 (s, 2H), 3.14 (s, 3H), 1.42 (s, 9H); IR (thin film) 3294, 2977, 1704, 1366, 1152 cm ^-1 ; ESIMS m / z 279 ([MH] ^- ).

塩化水素（ジオキサン中、４Ｎ、５．０ｍＬ）を、１−メチルヒドラジン−１，２−ジカルボン酸２−ベンジル１−ｔｅｒｔ−ブチル（Ｃ６５）（８．５ｇ、３０ｍｍｏｌ）のジオキサン（１００ｍＬ）溶液に加え、室温で２時間攪拌した。反応物を濃縮し、得られた残渣をペンタンで洗浄、ろ過し、真空下で乾燥させて、オフホワイト色の固形物（６．０ｇ、８７％）として表題化合物を得た：融点１６４〜１６６℃；¹H NMR (400 MHz, methanol-d₄) δ 7.53 - 7.18 (m, 5H), 5.25 (s, 2H), 2.93 (s, 3H); ¹³C NMR (101 MHz, DMSO-d₆) δ 153.79, 134.03, 126.98, 126.96, 126.73, 66.83, 34.14。 Example 28: Preparation of 2-methylhydrazine carboxylic acid benzyl hydrochloride (C66)

Hydrogen chloride (4N, 5.0 mL in dioxane) in a dioxane (100 mL) solution of 1-methylhydrazine-1,2-dicarboxylic acid 2-benzyl1-tert-butyl (C65) (8.5 g, 30 mmol). In addition, it was stirred at room temperature for 2 hours. The reaction was concentrated and the resulting residue was washed with pentan, filtered and dried under vacuum to give the title compound as an off-white solid (6.0 g, 87%): melting point 164-166. ℃; ¹ H NMR (400 MHz, methanol-d ₄ ) δ 7.53 --7.18 (m, 5H), 5.25 (s, 2H), 2.93 (s, 3H); ¹³ C NMR (101 MHz, DMSO-d ₆ ) δ 153.79, 134.03, 126.98, 126.96, 126.73, 66.83, 34.14.

２５０ｍＬの丸底フラスコに、トリホスゲン（１．９８ｇ、６．６６ｍｍｏｌ）のジクロロメタン（２０ｍＬ）溶液を加え、無色溶液を得た。反応物を−４０℃に冷却し、２，２，２−トリフルオロエチルアミン（２．００ｇ、２０．２ｍｍｏｌ）とトリエチルアミン（４．０９ｇ、４０．４ｍｍｏｌ）のジクロロメタン（１０ｍＬ）溶液を１時間かけて加えた。反応物をさらに３０分間、−４０℃で攪拌させた。２−メチルヒドラジンカルボン酸ベンジル塩酸塩（Ｃ６７）のジクロロメタン（３０ｍＬ）溶液を、この反応混合物に３０分かけて加え、反応混合物を室温まで加温させ、さらに２時間攪拌した。反応混合物を分液漏斗に移し、炭酸ナトリウム水溶液、水およびブラインで洗浄し、硫酸マグネシウム上で乾燥させ、ろ過し、濃縮して、黄色の液体として表題化合物（３．８ｇ、４０％）を得た。¹H NMR (300 MHz, DMSO-d₆) δ 9.50 (br s, 1H), 7.37 - 7.33 (m, 6H), 5.11 (s, 2H), 3.82 - 3.73 (m, 2H), 2.95 (s, 3H); IR (薄膜) 3332, 1735, 1161, 742 cm^-1; ESIMS m/z306.09 ([M+H]⁺)。 Example 29: Preparation of 2-Methyl-2-((2,2,2-trifluoroethyl) carbamoyl) hydrazinecarboxylic acid 2-benzyl (C67)

A solution of triphosgene (1.98 g, 6.66 mmol) in dichloromethane (20 mL) was added to a 250 mL round bottom flask to obtain a colorless solution. The reaction is cooled to −40 ° C. and a solution of 2,2,2-trifluoroethylamine (2.00 g, 20.2 mmol) and triethylamine (4.09 g, 40.4 mmol) in dichloromethane (10 mL) over 1 hour. added. The reaction was stirred for an additional 30 minutes at −40 ° C. A solution of 2-methylhydrazinecarboxylic acid benzyl hydrochloride (C67) in dichloromethane (30 mL) was added to the reaction mixture over 30 minutes, the reaction mixture was warmed to room temperature and stirred for an additional 2 hours. The reaction mixture is transferred to a separatory funnel, washed with aqueous sodium carbonate solution, water and brine, dried over magnesium sulphate, filtered and concentrated to give the title compound (3.8 g, 40%) as a yellow liquid. rice field. ^{1 1} H NMR (300 MHz, DMSO-d ₆ ) δ 9.50 (br s, 1H), 7.37 --7.33 (m, 6H), 5.11 (s, 2H), 3.82 --3.73 (m, 2H), 2.95 (s, 3H); IR (thin film) 3332, 1735, 1161, 742 cm ^-1 ; ESIMS m / z 306.09 ([M + H] ⁺ ).

パラジウム炭素（１０％，０．３０ｇ）を、Ｎ−（２，２，２−トリフルオロエチルカルバモイルアミノカルバミン酸ベンジル（Ｃ６７）（２．５ｇ、８．１９ｍｍｏｌ）のメタノール（３０ｍＬ）攪拌溶液に加えた。反応混合物を、水素雰囲気下（３０ｐｓｉ）、室温で１２時間攪拌した。反応混合物をろ過し、濃縮した。得られた固形物を１，４−ジオキサン（２０ｍＬ）に溶解させ、塩化水素（１，４−ジオキサン中、１Ｎ、２．５ｍＬ）を加えた。混合物を室温で１時間攪拌し、その後濃縮した。得られた固形物を酢酸エチルで洗浄し、減圧下で乾燥させ、白色の固形物（１．２ｇ、４４％）として表題化合物を得た：¹H NMR (300 MHz, DMSO-d₆) δ 9.40 (br s, 3H), 7.97 (br s, 1H), 3.94 - 3.78 (m, 2H), 3.13 (s, 3H); IR (薄膜) 3243, 1679, 1565, 1157, 648 cm-¹; ESIMS m/z 171.2 ([M]⁺)。 Example 30: Preparation of 1-methyl-N- (2,2,2-trifluoroethyl) hydrazinecarboxamide (C68)

Palladium on carbon (10%, 0.30 g) is added to a stirred solution of N- (2,2,2-trifluoroethylcarbamoylaminocarbamic acid benzyl (C67) (2.5 g, 8.19 mmol) in methanol (30 mL). The reaction mixture was stirred under a hydrogen atmosphere (30 psi) at room temperature for 12 hours. The reaction mixture was filtered and concentrated. The obtained solid was dissolved in 1,4-dioxane (20 mL) and hydrogen chloride (20 mL) was dissolved. 1N, 2.5 mL in 1,4-dioxane) was added. The mixture was stirred at room temperature for 1 hour and then concentrated. The resulting solid was washed with ethyl acetate, dried under reduced pressure and white. The title compound was obtained as a solid (1.2 g, 44%): ¹ H NMR (300 MHz, DMSO-d ₆ ) δ 9.40 (br s, 3H), 7.97 (br s, 1H), 3.94 --3.78 ( m, 2H), 3.13 (s, 3H); IR (thin film) 3243, 1679, 1565, 1157, 648 cm- ¹ ; ESIMS m / z 171.2 ([M] ⁺ ).

工程１。（Ｚ）−Ｎ’−メチル−４−（１，４，４，４−テトラフルオロ−３−（３，４，５−トリクロロフェニル）ブタ−１−エン−１−イル）ベンゾヒドラジド塩酸塩（ＣＣ３）：２５ｍＬのバイアルに、１−メチル−２−（４−（１，４，４，４−テトラフルオロ−３−（３，４，５−トリクロロフェニル）ブタ−１−エン−１−イル）ベンゾイル）ヒドラジンカルボン酸（Ｚ）−ｔｅｒｔ−ブチル（ＣＣ２）（０．１００ｇ、０．１８０ｍｍｏｌ）、塩化水素（ジオキサン中、４Ｍ、４ｍＬ）のジクロロメタン（０．９ｍＬ）溶液を加え、黄色溶液を得た。溶液を一晩攪拌した。反応物を濃縮し、残渣を直ちに次の工程で使用した。 Example 31: (Z) -1-methyl-2- (4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) ) Preparation of benzoyl) -N- (2,2,2-trifluoroethyl) hydrazinecarboxamide (FC1)

Process 1. (Z) -N'-methyl-4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) benzohydrazide hydrochloride ( CC3): In a 25 mL vial, 1-methyl-2- (4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) ) Benzoyl) Hydrazine Carboxylic acid (Z) -tert-butyl (CC2) (0.100 g, 0.180 mmol), hydrogen chloride (4M in dioxane, 4 mL) in dichloromethane (0.9 mL) is added to make a yellow solution. Obtained. The solution was stirred overnight. The reaction was concentrated and the residue was immediately used in the next step.

Step 2. (Z) -1-Methyl-2- (4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) benzoyl)- N- (2,2,2-trifluoroethyl) hydrazine carboxamide: in a 25 mL vial, (Z) -N'-methyl-4- (1,4,4,4-tetrafluoro-3- (3,4) , 5-Trichlorophenyl) Buta-1-en-1-yl) Benzohydrazide hydrochloride (CC3) (0.100 g, 0.203 mmol), diisopropylethylamine (0.142 mL, 0.813 mmol), and acetonitrile (2. 0 mL) was added to obtain a yellow solution. 4-Nitrophenyl carbamic acid (2,2,2-trifluoroethyl) (0.107 g, 0.406 mmol) was added and the reaction was stirred at room temperature overnight. The reaction was quenched with aqueous sodium bicarbonate solution, extracted with dichloromethane and purified by reverse phase flash column chromatography to give the title compound as a yellow oil (0.0321 g, 25%).

黄色の油状物（０．０６２ｇ、３４％）として単離した。 The following compounds were prepared in a manner similar to the procedure outlined in Example 31:
(Z) -1-Methyl-2- (2-methyl-4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) ) Benzoyl) -N- (2,2,2-trifluoroethyl) hydrazine carboxamide (F28)

It was isolated as a yellow oil (0.062 g, 34%).

以下の化合物を、実施例１に概説した手順と同様の方法で調製した：
（Ｚ）−４−（１，４，４，４−テトラフルオロ−３−（３，４，５−トリクロロフェニル）ブタ−１−エン−１−イル）−１−ナフトエ酸（Ｃ６９）

黄色の固形物（０．８５ｇ、５３％）として単離した：¹H NMR (300 MHz, CDCl₃) δ 8.30 (d, J = 7.5 Hz, 1H), 8.07 - 8.05 (m, 1H), 7.70 - 7.61 (m, 4H), 7.49 (s, 2H), 5.69 (dd, J = 9.9, 31.2 Hz, 1H), 4.75 - 4.69 (m, 1H); IR （薄膜) 3445, 1684, 1260, 750 cm^-1; ESIMS m/z475.23 ([M]^-)。 The following molecules in Table 1 can be prepared according to the disclosed procedures: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16, P17. , P18, P19, and P20
Table 1 Assumed molecular structure and preparation method

The following compounds were prepared in a manner similar to the procedure outlined in Example 1:
(Z) -4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) -1-naphthoic acid (C69)

Isolated as a yellow solid (0.85 g, 53%): ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.30 (d, J = 7.5 Hz, 1H), 8.07 --8.05 (m, 1H), 7.70 --7.61 (m, 4H), 7.49 (s, 2H), 5.69 (dd, J = 9.9, 31.2 Hz, 1H), 4.75 --4.69 (m, 1H); IR (thin film) 3445, 1684, 1260, 750 cm ^-1 ; ESIMS m / z475.23 ([M] ^- ).

褐色の固形物（１．０ｇ、４７％）として単離した：¹H NMR (300 MHz, DMSO-d₆) δ 13.80 (s, 1H), 8.17 - 8.12 (m, 3H), 7.91 - 7.86 (m, 3H), 6.87 (dd, J = 9.9, 36.0 Hz, 1H), 5.39 - 5.32 (m, 1H); ESIMS m/z 493.14 ([M-H]^-)。 (Z) -4- (3- (3-chloro-5- (trifluoromethyl) phenyl) -1,4,5,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoro) Methyl) Benzoic acid (C70)

Isolated as a brown solid (1.0 g, 47%): ¹ H NMR (300 MHz, DMSO-d ₆ ) δ 13.80 (s, 1H), 8.17 --8.12 (m, 3H), 7.91 --7.86 ( m, 3H), 6.87 (dd, J = 9.9, 36.0 Hz, 1H), 5.39 --5.32 (m, 1H); ESIMS m / z 493.14 ([MH] ^- ).

褐色のゴム状物（１．７ｇ、４２％）として単離した：¹H NMR (300 MHz, DMSO-d₆) δ 13.80 (s, 1H), 8.14 (s, 1H), 8.09 (d, J= 8.1 Hz, 1H), 7.91 (d, J = 8.1 Hz, 1H), 7.83 (s, 1H), 7.65 (s, 1H), 6.87 (dd, J = 9.9, 36.0 Hz, 1H), 5.13 - 5.07 (m, 1H), 2.42 (s, 3H); IR (薄膜) 3446, 2928, 1716 cm^-1; ESIMS m/z 473.10 ([M-H]^-)。 (Z) -4- (3- (3,4-dichloro-5-methylphenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoromethyl) Benzoic acid (C71)

Isolated as brown rubber (1.7 g, 42%): ¹ H NMR (300 MHz, DMSO-d ₆ ) δ 13.80 (s, 1H), 8.14 (s, 1H), 8.09 (d, J) = 8.1 Hz, 1H), 7.91 (d, J = 8.1 Hz, 1H), 7.83 (s, 1H), 7.65 (s, 1H), 6.87 (dd, J = 9.9, 36.0 Hz, 1H), 5.13 --5.07 (m, 1H), 2.42 (s, 3H); IR (thin film) 3446, 2928, 1716 cm ^-1 ; ESIMS m / z 473.10 ([MH] ^- ).

オフホワイト色の固形物（０．７０ｇ、５２％）として単離した：融点１５４〜１５６℃：¹H NMR (400 MHz, DMSO-d₆) δ 13.40 (br s, 1H), 8.88 - 8.84 (m, 1H), 8.17 - 8.10 ( m, 2H), 7.75 - 7.66 (m, 3H), 5.39 (dd, J = 3.6, 17.2 Hz, 1H), 5.23 (dd, J = 36.0, 50.4 Hz, 1H); ESIMS m/z 215.20 ([M-H]^-)。 The following compounds were prepared in a manner similar to the procedure outlined in Example 7.
(4- (1-Fluorovinyl) -1-naphthoic acid (C72)

Isolated as an off-white solid (0.70 g, 52%): Melting point 154 to 156 ° C: ^{1 1} H NMR (400 MHz, DMSO-d ₆ ) δ 13.40 (br s, 1H), 8.88 --8.84 ( m, 1H), 8.17 --8.10 (m, 2H), 7.75 --7.66 (m, 3H), 5.39 (dd, J = 3.6, 17.2 Hz, 1H), 5.23 (dd, J = 36.0, 50.4 Hz, 1H) ESIMS m / z 215.20 ([MH] ^- ).

透明の油状物（６．７ｇ、６７％）として単離した：¹H NMR (300 MHz, CDCl₃) δ 7.46 (s, 1H), 7.28 (s, 1H), 5.02 (q, J = 7.2 Hz, 1H), 2.45 (s, 3H); IR (薄膜) 1260, 1113, 750 cm^-1; EIMS m/z 322 ([M]⁺)。 The following compounds were prepared in a manner similar to the procedure outlined in Example 8.
5- (1-bromo-2,2,2-trifluoroethyl) -1,2-dichloro-3-methylbenzene (C76)

Isolated as clear oil (6.7 g, 67%): ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.46 (s, 1H), 7.28 (s, 1H), 5.02 (q, J = 7.2 Hz) , 1H), 2.45 (s, 3H); IR (thin film) 1260, 1113, 750 cm ^-1 ; EIMS m / z 322 ([M] ⁺ ).

淡黄色の油状物（４．６ｇ、７９％）として単離した：¹H NMR (300 MHz, CDCl₃) δ 7.44 (s, 1H), 7.26 (s, 1H), 4.97 (q, J = 6.6 Hz, 1H), 2.44 (s, 3H); IR (薄膜) 3428, 1275, 1262, 750 cm^-1; EIMS m/z 258 ([M]⁺)。以下の化合物を、実施例１３に概説しされる手順と同様の方法で調製した：
（Ｚ）−２−（４−（３−（３−ブロモ−４−クロロフェニル）−１，４，４，４−テトラフルオロブタ−１−エン−１−イル）−２−（トリフルオロメチル）ベンゾイル）−１−メチルヒドラジン−１−カルボン酸ｔｅｒｔ−ブチル（Ｃ７３）

無色のゴム状物（０．４００ｇ、５５％）として単離した：¹H NMR (300 MHz, CDCl₃) δ 7.88 (s, 1H), 7.79 (d, J = 7.5 Hz, 1H), 7.68 (d, J = 1.9 Hz, 1H), 7.50 - 7.47 (m, 2H), 7.30 (dd, J = 1.9, 8.4 Hz, 1H), 6.62 (dd, J = 9.9, 32.7 Hz, 1H), 4.69 - 4.57 (m, 1H), 3.44 (s, 3H) 1,47 (s, 9H); ESIMS m/z 534.09 ([M-CO₂C₄H₉]⁺)。 The following compounds were prepared in a manner similar to the procedure outlined in Example 10:
1- (3,4-dichloro-5-methylphenyl) -2,2,2-trifluoroethane-1-ol (C77)

Isolated as a pale yellow oil (4.6 g, 79%): ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.44 (s, 1H), 7.26 (s, 1H), 4.97 (q, J = 6.6) Hz, 1H), 2.44 (s, 3H); IR (thin film) 3428, 1275, 1262, 750 cm ^-1 ; EIMS m / z 258 ([M] ⁺ ). The following compounds were prepared in a manner similar to the procedure outlined in Example 13.
(Z) -2- (4- (3- (3-Bromo-4-chlorophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (trifluoromethyl) Benzoyl) -1-methylhydrazine-1-carboxylate tert-butyl (C73)

Isolated as colorless rubber (0.400 g, 55%): ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.88 (s, 1H), 7.79 (d, J = 7.5 Hz, 1H), 7.68 ( d, J = 1.9 Hz, 1H), 7.50 --7.74 (m, 2H), 7.30 (dd, J = 1.9, 8.4 Hz, 1H), 6.62 (dd, J = 9.9, 32.7 Hz, 1H), 4.69 --4.57 (m, 1H), 3.44 (s, 3H) 1,47 (s, 9H); ESIMS m / z 534.09 ([M-CO ₂ C ₄ H ₉ ] ⁺ ).

褐色の固形物（０．０４０ｇ、２２％）として単離した。 The following compounds were prepared in a manner similar to the procedure outlined in Example 14.
(Z) -2- (4- (3- (3-chloro-5- (trifluoromethyl) phenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (Trifluoromethyl) Benzoyl) -1-Methyl-N- (2,2,2-trifluoroethyl) Hydrazine-1-carboxamide (PF9)

It was isolated as a brown solid (0.040 g, 22%).

黄色の固形物（０．１２ｇ、４２％）として単離した。 The following compounds were prepared in a manner similar to the procedure outlined in Example 15.
(Z) -2- (4- (3- (3,4-dichloro-5-methylphenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- (tri) Fluoromethyl) benzoyl) -1-methyl-N- (2,2,2-trifluoroethyl) hydrazine-1-carboxamide (F30)

It was isolated as a yellow solid (0.12 g, 42%).

黄色のゴム状物（０．０７０ｇ、３４％）として単離した。 (Z) -1-Methyl-2- (4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) -1-yl) -1- Naftyl) -N- (2,2,2-trifluoroethyl) hydrazine-1-carboxamide (PF1)

It was isolated as a yellow rubbery substance (0.070 g, 34%).

黄色のガラス状物（０．０５８ｇ、６０％）として単離した。 The following compounds were prepared in a manner similar to the procedure outlined in Example 16:
(Z) -N'-Pivaloyl-4- (1,4,4,4-tetrafluoro-3- (3,4,5-trichlorophenyl) buta-1-ene-1-yl) -2- (tri) Fluoromethyl) benzohydrazide (F29)

It was isolated as a yellow glass (0.058 g, 60%).

無色のゴム状物（０．２５０ｇ、７４％）として単離した：ESIMS m/z 535.13 ([M+H]⁺)。 The following compounds were prepared in a manner similar to the procedure outlined in Example 21:
(Z) -4- (3- (3-Bromo-4-chlorophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -N'-methyl-2- (trifluoro) Methyl) benzohydrazide hydrochloride (C74)

Isolated as a colorless rubbery material (0.250 g, 74%): ESIMS m / z 535.13 ([M + H] ⁺ ).

４−ブロモ‐１−ナフトエ酸（２．５０ｇ、９．９８ｍｍｏｌ）のジメチルスルホキシド（３２．３ｍＬ）の攪拌溶液に、ビニルトリフルオロホウ酸カリウム（１．３３ｇ、９．９６ｍｍｏｌ）、炭酸カリウム （３．８５ｇ、２７．９ｍｍｏｌ） および［１，１′−ビス（ジフェニルホスフィノ）フェロセン］−ジクロロパラジウム（ＩＩ）（０．３６４ｇ、０．４９８ｍｍｏｌ）を加えた。反応混合物を８０℃の水槽で１８時間加熱した。反応混合物を周辺温度まで冷却し、１Ｎの塩酸水溶液（１５０ｍＬ）と水（１５０ｍＬ）で希釈した。混合物を酢酸エチルで抽出した。有機層をブラインで洗浄して、硫酸ナトリウムで乾燥し、減圧下で濃縮して粗製化合物を得た。この粗化合物をカラムクロマトグラフィー（ＳｉＯ_２、ヘキサン中、０〜１００％の酢酸エチルで溶出）により精製し、明黄色固形物として表題化合物を得た（１．３６ｇ、６２％）：融点１４７〜１５５℃；¹H NMR (300 MHz, acetone-d₆) δ 11.42 (s, 1H), 9.16 - 9.03 (m, 1H), 8.31 - 8.25 (m, 2H), 7.77 (dd, J = 7.7, 0.7 Hz, 1H), 7.70 - 7.57 (m, 3H), 5.95 (dd, J = 17.2, 1.5 Hz, 1H), 5.62 (dd, J = 11.1, 1.5 Hz, 1H); ESIMS m/z 197.1 ([M-H]^-)。 Example 32: Preparation of 4-vinyl-1-naphthoic acid (C75)

In a stirred solution of 4-bromo-1-naphthoic acid (2.50 g, 9.98 mmol) in dimethyl sulfoxide (32.3 mL), potassium vinyltrifluoroborate (1.33 g, 9.96 mmol), potassium carbonate (3.85 g, 27.9 mmol) And [1,1'-bis (diphenylphosphino) ferrocene] -dichloropalladium (II) (0.364 g, 0.498 mmol) were added. The reaction mixture was heated in a water tank at 80 ° C. for 18 hours. The reaction mixture was cooled to ambient temperature and diluted with 1N aqueous hydrochloric acid solution (150 mL) and water (150 mL). The mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate and concentrated under reduced pressure to give the crude compound. This crude compound was purified by column chromatography (eluting _{with 0-100% ethyl acetate in SiO 2} , hexane) to give the title compound as a bright yellow solid (1.36 g, 62%): melting point 147-. 155 ° C; ¹ H NMR (300 MHz, hexane-d ₆ ) δ 11.42 (s, 1H), 9.16 --9.03 (m, 1H), 8.31 --8.25 (m, 2H), 7.77 (dd, J = 7.7, 0.7 Hz, 1H), 7.70 --7.57 (m, 3H), 5.95 (dd, J = 17.2, 1.5 Hz, 1H), 5.62 (dd, J = 11.1, 1.5 Hz, 1H); ESIMS m / z 197.1 ([MH) ] ^- ).

（Ｚ）−４−（３−（３−ブロモ−４−クロロフェニル）−１，４，４，４−テトラフルオロブタ−１−エン−１−イル）−Ｎ’−メチル−２−（トリフルオロメチル）ベンゾヒドラジド塩酸塩（Ｃ７４）（０．２００ｇ、０．３５ｍｍｏｌ）のアセトニトリル（１０ｍＬ）攪拌溶液に、（２，２，２−トリフルオロエチル）カルバミン酸４−ニトロフェニル（０．１７５ｇ、０．７０ｍｍｏｌ）とジイソプロピルエチルアミン（０．１８１ｇ、１．４ｍｍｏｌ）を加えた。反応混合物を室温で６時間攪拌し、その後、水とジクロロメタンの間で分離させた。有機層をブラインで洗浄し、硫酸ナトリウム上で乾燥させ、減圧下で濃縮し、粗化合物を得た。カラムクロマトグラフィー（ＳｉＯ_２、石油エーテル中、３０％酢酸エチルで溶出）で精製して、表題化合物を淡黄色のゴム状物（０．１０５ｇ、４０％）として得た。 Example 33: (Z) -2- (4- (3- (3-bromo-4-chlorophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -2- ( Preparation of trifluoromethyl) benzoyl) -1-methyl-N- (2,2,2-trifluoroethyl) hydrazine-1-carboxamide (PF8)

(Z) -4- (3- (3-Bromo-4-chlorophenyl) -1,4,4,4-tetrafluorobuta-1-ene-1-yl) -N'-methyl-2- (trifluoro) 4-Nitrophenyl (2,2,2-trifluoroethyl) carbamate (0.175 g, 0) in a stirred solution of acetonitrile (10 mL) of methyl) benzohydrazide hydrochloride (C74) (0.200 g, 0.35 mmol). .70 mmol) and diisopropylethylamine (0.181 g, 1.4 mmol) were added. The reaction mixture was stirred at room temperature for 6 hours and then separated between water and dichloromethane. The organic layer was washed with brine, dried over sodium sulfate and concentrated under reduced pressure to give the crude compound. Purification by column chromatography (SiO ₂ , eluted with 30% ethyl acetate in petroleum ether) gave the title compound as a pale yellow rubbery product (0.105 g, 40%).

窒素下、氷槽で冷却した５−ブロモ−１，２−ジクロロ−３−メチルベンゼン（６．９ｇ、２９ｍｍｏｌ）のテトラヒドロフラン（６５ｍＬ）溶液に、塩化イソプロピルマグネシウム塩化リチウム錯体のテトラヒドロフラン（２６．８ｍＬ、３４．８ｍｍｏｌ）溶液を加えた。１時間後、２，２，２−トリフルオロ酢酸メチル（３．７９ｍＬ、３７．７ｍｍｏｌ）を加えた。３０分後、氷槽を取り除き、溶液を１時間撹拌した。反応混合物を塩酸水溶液（２Ｎ）でクエンチした。混合物を濃縮し、ジクロロメタンで抽出した。有機層をブラインで洗浄して、硫酸ナトリウム上で乾燥させ、濾過及び濃縮した。カラムクロマトグラフィ（ＳｉＯ_２、石油エーテル）で精製することにより、表題化合物を白色固形物（５．９ｇ、８０％）として得た：¹H NMR (400 MHz, CDCl₃) δ 8.00 (s, 1H), δ 7.83(s, 1H), 2.51 (s, 3H); EIMS m/z 256 ([M]⁺)。 Example 34: Preparation of 1- (3,4-dichloro-5-methylphenyl) -2,2,2-trifluoroethane-1-one (C78)

In a solution of 5-bromo-1,2-dichloro-3-methylbenzene (6.9 g, 29 mmol) in tetrahydrofuran (65 mL) cooled in an ice bath under nitrogen, tetrahydrofuran (26.8 mL) of the lithium chloride lithium chloride complex, 34.8 mmol) solution was added. After 1 hour, methyl 2,2,2-trifluoroacetate (3.79 mL, 37.7 mmol) was added. After 30 minutes, the ice tank was removed and the solution was stirred for 1 hour. The reaction mixture was quenched with aqueous hydrochloric acid (2N). The mixture was concentrated and extracted with dichloromethane. The organic layer was washed with brine, dried over sodium sulfate, filtered and concentrated. Purification by column chromatography (SiO ₂ , petroleum ether) gave the title compound as a white solid (5.9 g, 80%): ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.00 (s, 1 H). , δ 7.83 (s, 1H), 2.51 (s, 3H); EIMS m / z 256 ([M] ⁺ ).

Bioassay Beet armyworm (Spodoptera exigua), Iraksakin uwaba (Trichoplusia ni), Corn earworm (Helicoverpa zea) Helicoverpaz The following bioassays for (Myzus persicae) and Nettai Shimaka (Aedes aegipti) are included herein. In addition, Beet armyworm, Corn earworm and Nettle nettle are three good indicator species against a wide range of chewing pests. In addition, Myzus persicae is a good indicator species against a wide range of sap-feeding pests. Results using these four indicator species and Aedes aegypti show the broad usefulness of the molecule of formula 1 in the control of pests of the phylum Arthropod, Mollusk, and C. elegans (for further information, Methods for). The Designing and Optimization of New Active Ingredients, Modeln Methods in Crop Protection Research, Edited by Jeschke, P., Kramer, W.M.

Example A: Beet armyworm (Spodoptera exigua (LAPHEG)) (“BAW”), Corn earworm (Helicoverpa zea, HELIZE) (“CEW”), and nettle looper (“CEW”), and nettle looper. Bioassay for D (Trichoplusia ni, TRIPNI) (“CL”).

Shiroichimojiyoto is a serious pest of financial concern for alfalfa, asparagus, beets, citrus fruits, corn, cotton, onions, peas, peppers, potatoes, soybeans, sugar beets, sunflowers, tobacco and tomatoes. be. Native to Southeast Asia, it is now found in Africa, Australia, Japan, North America, and Southern Europe. Larvae feed in swarms and can cause catastrophic crop loss. It is known to be resistant to some pesticides.

The cabbage looper is a serious pest found all over the world. Among the crops, this is alfalfa, bean, beetroot, broccoli, Brussels sprouts, cabbage, cantaloupe, califurawa, celery, collard, cotton, cucumber, eggplant, kale, lettuce, melon, mustard greens, parsley, pea, pepper, potato, Attacks soybeans, kale, pumpkins, tomatoes, cubs, and watermelons. This species is extremely harmful to plants due to its large diet. Larvae feed on three times their body weight daily. The feeding ground is marked by a large accumulation of sticky, moist fecal material. It is known to be resistant to some pesticides.

Some consider the corn earworm to be the most damaging crop pest in North America. This pest attacks beneficial crops and the harvested portion of the crop. Among the crops, this pest is alfalfa, artichoke, asparagus, cabbage, cantaloupe, collard, corn, cotton, sweet potato, cucumber, eggplant, lettuce, lima bean, melon, okra, pea, pepper, potato, pumpkin, green bean. , Soybeans, spinach, squash, sugar cane, sweet potatoes, tomatoes, and watermelons. In addition, the pest is known to be resistant to certain pesticides.

Therefore, it is important to control these pests due to the above factors. In addition, molecules that control these pests (BAW, CEW and CL), known as biting pests, are also beneficial in controlling other pests that bite plants.

The specific molecules disclosed in this document have been validated against BAW, CEW and CL using the procedures described in the Examples below. In reporting the results, we used the "BAW, CEW and CL Evaluation Tables" (see Table section).

Bioassays for BAW Bioassays for BAWs were performed using a 128-well diet tray assay. 1-5 second instar BAW larvae were placed in each well (3 mL) of the diet tray. Each well was previously filled with 1 mL of artificial diet, 50 μg / cm ² of test molecule (dissolved in 50 μL of 90:10 acetone-water mixture) was added (to each of the 8 wells) and then dried. The tray was covered with a clear self-adhesive cover and kept at 25 ° C. at 14:10 light-dark for 5-7 days. Mortality was recorded for larvae in each well and then activity in 8 wells was averaged. The results are shown in a table entitled "Table ABC: Biological Results" (see Table section).

Bioassays for CL Bioassays for CL were performed using a 128-well diet tray assay. 1-5 second instar CL larvae were placed in each well (3 mL) of the diet tray. Each well was previously filled with 1 mL of artificial diet, 50 μg / cm ² of test molecule (dissolved in 50 μL of 90:10 acetone-water mixture) was added (to each of the 8 wells) and then dried. The tray was covered with a clear self-adhesive cover and kept at 25 ° C. at 14:10 light-dark for 5-7 days. Mortality was recorded for larvae in each well and then activity in 8 wells was averaged. The results are shown in a table entitled "Table ABC: Biological Results" (see Table section).

Example B: Bioassay for Myzus persicae (Myzus persicae, MYZUPE) (“GPA”).

GPA is the most influential aphid pest of peach trees, resulting in slow growth, leaf deflation, and death of various tissues. GPA is also used to transport plant viruses such as potato virus Y and potato leaf curl disease virus to members of the Solanaceae Solanaceae, and to transport various mosaic viruses to many other food crops. It is harmful because it acts as a mediator. GPA attacks plants such as broccoli, burdock, cabbage, carrot, califlora, radish, eggplant, green beans, lettuce, macadamia, papaya, pepper, sweet potato, tomato, creson and zucchini. GPA also attacks many ornamental crops such as carnations, chrysanthemums, flowering white cabbage, poinsettia, and roses. GPA develops resistance to many pesticides. Therefore, it is important to control this pest due to the above factors. In addition, molecules that control this pest (GPA), known as sap-eating pests, are also beneficial in controlling other sap-feeding pests from plants.

The specific molecules disclosed in this document were tested against GPA using the procedures described in the Examples below. In reporting the results, we used the “GPA and YFM Evaluation Table” (see Table section).

Cabbage seedlings grown in 3-inch pots and having 2-3 small (3-5 cm) true leaves were used as test culture medium. One day prior to chemical application, seedlings were invaded by 20-50 GPAs (wingless adults and larvae). Four pots with individual seedlings were used for each treatment. The test molecule (2 mg) was dissolved in 2 mL of acetone / methanol (1: 1) solvent to form a storage solution of 1000 ppm of the test molecule. The storage solution was diluted 5-fold with 0.025% aqueous Tween 20 solution to give a solution of 200 ppm test molecules. A handheld aspirator sprayer was used to spray the solution until it ran down on both sides of the cabbage leaves. The reference plant (solvent test) was sprayed with a diluent containing only 20% by volume acetone / methanol (1: 1) solvent. Treated plants were kept in a retention chamber at about 25 ° C. and ambient relative humidity (RH) for 3 days before categorization. Evaluation was performed by counting the number of viable aphids per plant under a microscope. Control rate using the following Abbott correction formula (WS Abbott, "A Method of Computing the Effects of an Insecticide" J. Econ. Entomol. 18 (1925), pp. 265-267). bottom.

Corrected control rate (%) = 100 * (XY) / X
During the ceremony
x = Number of viable aphids on solvent-tested plants Y = Number of viable aphids on treated plants The results are shown in the table entitled "Table ABC: Biological Results" (see Table section).

Example C: Bioassay on Aedes aegypti, AEDSAE (“YFM”) YFM prefers to feed on humans during the day and may be found in or near human settlements. Most often. YFM is a vector that transmits several diseases. It is a mosquito that can spread the dengue and yellow fever viruses. Yellow fever is the second most dangerous mosquito-borne disease after malaria. Yellow fever is an acute viral bleeding disorder, and if left untreated, up to 50% of severely affected people will die from yellow fever. Yellow fever causes an estimated 200,000 cases worldwide each year and causes 30,000 deaths. Dengue fever is a troublesome viral disease. It is sometimes referred to as "fracture fever" or "break-heart fever" because of the intense pain it can cause. Dengue kills about 20,000 people each year. Therefore, it is important to control this pest due to the above factors. In addition, molecules that control this pest (YFM), known as hematophageous pests, are beneficial in controlling other pests that cause distress in humans and animals.

The specific molecules disclosed in this document were tested against YFM using the procedures described in the following paragraphs. In reporting the results, we used the “GPA and YFM Evaluation Table” (see Table section).

A master plate containing 400 μg of molecules (corresponding to 4000 ppm solution) dissolved in 100 μL of dimethyl sulfoxide (DMSO) is used. The master plate of the collected molecules contains 15 μL per well. For this plate, 135 μL of 90:10 water / acetone mixture is added to each well. A robot (Biomek® NXP Laboratory Automation Workstation) is programmed to dispense 15 μL of aspirate into an empty 96-well shallow plate (“daughter” plate) from the master plate. Six replicas (“daughter” plates) are made per master. Subsequently, the prepared daughter plate is immediately invaded with YFM larvae.

The day before the plate should be processed, mosquito eggs are placed in Millipore water containing liver powder to initiate hatching (4 g in 400 mL). After making daughter plates using a robot, they are invaded with 220 μL of liver powder / larval mosquito mixture (about 1 day old larvae). After invading the plate with mosquito larvae, a non-evaporative lid is used to cover the plate to prevent desiccation. The plates are kept at room temperature for 3 days before categorization. After 3 days, observe each well and determine the assessment based on mortality. The results are shown in a table entitled "Table ABC: Biological Results" (see Table section).

Agriculturally acceptable acid addition salts, salt derivatives, solvates, ester derivatives, polymorphs, isotopes and radionuclides The molecules of formula 1 can be agriculturally acceptable acid addition salts. As a non-limiting example, amine functional groups include hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, acetic acid, benzoic acid, citric acid, malonic acid, salicylic acid, malic acid, fumaric acid, oxalic acid, succinic acid, tartrate acid. , Lactic acid, gluconic acid, ascorbic acid, maleic acid, aspartic acid, benzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, hydroxymethanesulfonic acid, and hydroxyethanesulfonic acid can form salts. Furthermore, as a non-limiting example, acid functional groups can form salts containing salts derived from alkali metals or alkaline earth metals as well as salts derived from ammonia and amines. Examples of preferred cations include sodium, potassium, and magnesium.

The molecule of formula 1 can be a salt derivative. As a non-limiting example, salt derivatives can be prepared by contacting the free base with a sufficient amount of the desired acid to form a salt. Free bases can be regenerated by treating the salt with a diluted aqueous solution of the appropriate base, such as a diluted aqueous solution of sodium hydroxide, potassium carbonate, ammonia, and sodium hydrogen carbonate. As an example, pesticides, such as 2,4-D, are often made more water soluble by converting them to their dimethylamine salts.

The molecule of formula 1 may be formulated into a stable complex with a solvent, which causes the complex to remain intact after removal of the uncomplexed solvent. These complexes are often referred to as "solvates". On the other hand, it is particularly desirable to form a stable hydrate with water as a solvent.

The molecule of formula 1 can be an ester derivative. Moreover, these ester derivatives can be applied in the same way that the molecules disclosed herein were applied.

The molecule of formula 1 can be prepared as various crystalline polymorphs. Polymorphism is important in the development of agricultural chemicals, as different crystalline polymorphs or structures of the same molecule can have significantly different physical properties and biological performance.

The molecule of formula 1 can be made with different isotopes. Of particular importance are molecules that have ² H (also known as deuterium) or ^{3 H (also known as tritium) instead of 1 H.} The molecule of formula 1 can be made from different radionuclides. Of particular importance are molecules with ^{14 C.} The use of molecules of formula 1 with deuterium, tritium, or ¹⁴ C in biological studies may allow tracking in chemical and physiological processes, half-life studies, and MoA studies. ..

The molecule of steric isomer formula 1 can exist as one or more steric isomers. Therefore, a particular molecule can be produced as a racemic mixture. Those skilled in the art will appreciate that one stereoisomer may be more active than the other. The individual character isomers can be obtained by known individual synthetic procedures, by conventional synthetic procedures with split starting materials, or by conventional split procedures. The particular molecule disclosed herein can exist as two or more isomers. The various isomers include geometric isomers, diastereomers, and enantiomers. Thus, the molecules disclosed herein include geometric isomers, racemic mixtures, individual stereoisomers, and optically active mixtures. Those skilled in the art will appreciate that one isomer may be more active than the other. The structures disclosed in this disclosure are depicted in only one geometry for clarity, but are intended to represent all geometry of the molecule.

Combination In another embodiment of the invention, the molecule of formula 1 can be used in combination with one or more active ingredients (eg, in compositional mix, or in simultaneous or sequential application).

In another embodiment of the invention, the molecule of formula 1 is combined with one or more active ingredients that are the same as, similar to, or perhaps different from the MoA of the molecule of formula 1 (eg,). It can be used in a mixed composition or in simultaneous or sequential application.
In another embodiment, the molecule of formula 1 has acaricidal properties, algae-killing properties, bird-killing properties, fungicidal properties, fungicidal properties, herbicidal properties, insecticidal properties, mollusk extermination properties, nematode-killing properties, and rodent-killing properties. And / or can be used in combination with one or more molecules with antimicrobial properties (eg, in compositional mix or in simultaneous or sequential application).

In another embodiment, the molecule of formula 1 is a feeding inhibitor, avian repellent, a chemical fertility agent, a herbicide toxicity palliative, an insect attractant, an insect repellent, a mammalian repellent, a mating inhibitor, a plant activity. It can be used in combination with one or more molecules that are agents, plant growth inhibitors, and / or synergists (eg, in compositional mix, or in simultaneous or sequential application).

In another embodiment, the molecule of formula 1 can be used in combination with one or more biopesticides (eg, in compositional mix, or in simultaneous or sequential application).

In another embodiment, various weight ratios can be used for the combination of the molecule of formula 1 and the active ingredient in the pesticide composition. For example, in a two-component mixture, the weight ratio of the molecule of formula 1 to the active ingredient may be about 100: 1 to about 1: 100, in another example the weight ratio is about 50: 1 to about 1:50. In another example, the weight ratio may be about 20: 1 to about 1/20, and in another example, the weight ratio may be about 10: 1 to about 1:10. In another example the weight ratio may be from about 5: 1 to about 1: 5, in another example the weight ratio may be from about 3: 1 to about 1: 3, and in another example the weight ratio. May be about 2: 1 to about 1: 2, and in the last example the weight ratio may be about 1: 1 (see Table B). However, in general, the weight ratio is preferably smaller than about 10: 1 to about 1:10. It may also be preferable to use a mixture of three or four ingredients, including the molecule of formula 1 and one or more active ingredients.

式１の分子と活性成分との重量比は、Ｘ：Ｙとして表されてもよく、ここで、Ｘは式１の分子の重量部であり、Ｙは活性成分の重量部である。Ｘの重量部の数値範囲は、０＜Ｘ≦１００であり、Ｙの重量部の数値範囲は、０＜Ｙ≦１００であり、表Ｃに図式的に示している。非限定的な例として、式１の分子と活性成分との重量比は２０：１であってもよい。 Table B

The weight ratio of the molecule of formula 1 to the active ingredient may be expressed as X: Y, where X is the weight portion of the molecule of formula 1 and Y is the weight portion of the active ingredient. The numerical range of the weight part of X is 0 <X ≦ 100, and the numerical range of the weight part of Y is 0 <Y ≦ 100, which are shown graphically in Table C. As a non-limiting example, the weight ratio of the molecule of formula 1 to the active ingredient may be 20: 1.

式１の分子と活性成分との重量比の範囲をＸ_１：Ｙ_１〜Ｘ_２：Ｙ_２で表すことができ、ここで、Ｘ及びＹは上記のように定義される。 Table C

The range of the weight ratio of the molecule of the formula 1 to the active ingredient _{can be expressed by X 1} : Y _{1 to} X ₂ : Y ₂ , where X and Y are defined as described above.

In one embodiment, the range of weight ratios may be X ₁ : Y _{1 to} X ₂ : Y ₂ , where X ₁ > Y ₁ and X ₂ <Y ₂ . As a non-limiting example, the range of the weight ratio of the molecule of the formula 1 to the active ingredient may be 3: 1 to 1: 3 (including endpoints).

In another embodiment, the range of weight ratios may be X ₁ : Y _{1 to} X ₂ : Y ₂ , where X ₁ > Y ₁ and X ₂ > Y ₂ . As a non-limiting example, the range of the weight ratio of the molecule of Formula 1 to the active ingredient may be 15: 1-3: 1 (including endpoints).

In another embodiment, the range of weight ratios is X ₁ : Y _{1 to} X ₂ : Y ₂ , where X ₁ <Y ₁ and X ₂ <Y ₂ . As a non-limiting example, the range of the weight ratio of the molecule of the formula 1 to the active ingredient may be about 1: 3 to about 1:20 (including endpoints).

Pharmaceuticals Agricultural chemicals are rarely suitable for application in their pure form. It is usually necessary to use the pesticide in the required concentration and in the proper form to add other substances to facilitate application, treatment, transport, storage and to provide maximum pesticide action. Therefore, pesticides include, for example, bait, concentrated emulsions, powders, emulsions, smokers, gels, granules, microencapsulants, seed treatments, suspension concentrates, suspo emulsions, tablets, etc. Formulated in water-soluble liquids, water-dispersible granules or dry flowables, wettable powders, and minimal solutions.

Pesticides are most often applied as aqueous suspensions or emulsions prepared from concentrated formulations of these pesticides. Such water-soluble, water-suspendable, or emulsifying preparations are solids commonly known as wettable powders, or water-dispersible granules, or liquids commonly known as emulsions, or aqueous suspensions. It is one of the turbid liquids. The wettable powder may be compressed to form water-dispersible granules and comprises a homogeneous mixture of pesticides, carriers and surfactants. The concentration of pesticides is generally from about 10% to about 90% by weight. The carrier is usually selected from attapulsite clay, montmorillonite clay, diatomaceous earth, or purified silicate. Effective surfactants that make up about 0.5% to about 10% of wettable powders are sulfonated lignins, condensed naphthalene sulfonates, naphthalene sulfonates, alkylbenzene sulfonates, alkyl sulphates, and nonionic surfactants ( It is found in (such as ethylene oxide adducts of alkylphenols).

Agricultural chemical emulsions have an easy-to-use concentration, such as a liquid of about 50 g / L to about 500 g / L, dissolved in a carrier that is either a water-miscible solvent or a mixture of a water-immiscible organic solvent and an emulsifier. Contains pesticides. Useful organic solvents include aromatics, especially xylene and petroleum fractions, especially high boiling naphthalene and olefin moieties of petroleum (such as heavy aromatic naphtha). Other organic solvents such as terpene solvents containing rosin derivatives, aliphatic ketones (such as cyclohexanone), and complex alcohols (such as 2-ethoxyethanol) can also be used. Suitable emulsifiers for emulsions are selected from conventional anionic and nonionic surfactants.

Aqueous suspensions include suspensions of water-insoluble pesticides dispersed in an aqueous carrier at a concentration of about 5% to about 50% by weight. Suspensions are prepared by finely grinding the pesticide and mixing it vigorously into a carrier composed of water and a surfactant. In addition, inorganic salts and components such as synthetic rubber or natural gum may be added to increase the density and viscosity of the aqueous carrier. It is often most effective to grind and mix the pesticide at the same time by preparing an aqueous mixture and homogenizing it in a device such as a sand mill, ball mill or piston homogenizer.

The pesticide can also be applied as a granular composition that is particularly useful for soil applications. Granular compositions usually contain from about 0.5% to about 10% by weight of pesticides dispersed in a carrier containing clay or a similar substance. Such compositions are generally prepared by dissolving the pesticide in a suitable solvent and applying it to a preformed granule carrier to a suitable particle size of about 0.5 to about 3 mm. .. Such compositions can also be formulated by making a dough or paste of the carrier and the molecule, grinding and drying to obtain the desired granular particle size.

Powders containing pesticides are prepared by homogeneously mixing the pesticides in powder form with suitable powdered agricultural carriers such as kaolin clay and ground volcanic rocks. The powder may preferably contain from about 1% to about 10% pesticide. The powder can be applied as a seed powder coat or as a foliar spray using a powder blower.

It is also practical to apply pesticides in the form of solutions, such as spray oils, using suitable organic solvents widely used in agricultural chemistry, usually petroleum.

Agricultural chemicals can also be applied in the form of aerosol compositions. In such compositions, the pesticide is dissolved or dispersed in a carrier that is a pressure generating spray mixture. The aerosol composition is packaged in a container from which the mixture is supplied via a spray valve.

Pesticide baits are formed when pesticides are mixed with food and / or attractants. When pests eat bait, they also ingest pesticides. The bait agent can be in the form of granules, gels, flowable powders, liquids or solids. The bait agent can be used in the hiding place of pests.

Fumigants are pesticides that have a relatively high vapor pressure and can therefore be present as a gas at a concentration sufficient to kill pests in soil or confined spaces. The toxicity of fumigants is proportional to their concentration and exposure time. They are characterized by excellent diffusivity and act upon penetration of pests into the respiratory system or absorption of pests through the epidermis. Fumigants are applied in airtight rooms or buildings, or in special chambers, under gas-impermeable sheets to control pests on stored products.

Pesticides can be microencapsulated by suspending pesticide particles or pesticide droplets in various types of plastic polymers. Microcapsules of various sizes, solubilities, wall thicknesses, and penetrances can be formed by changing the chemistry of the polymer or by changing the factors in processing. These factors control the rate at which the active ingredient is released, which affects residual performance, rate of action, and product odor.

The oil concentrate is made by dissolving the pesticide in a solvent that holds the pesticide in solution. Agricultural oils usually knock down and kill pests faster than other formulations by increasing the rate of pesticide uptake by dissolving the waxy coating on the exodermis and the solvent itself having pesticide action. Let me. Other advantages of the oil agent include excellent storage stability, excellent penetration into gaps, and excellent adhesion to oily surfaces.

Another embodiment is an oil-in-water emulsion, wherein the emulsion comprises oily globules, each with a layered liquid crystal coating and dispersed in the aqueous phase, each oily globules. It comprises at least one molecule that is agriculturally active and individually coated with a monolamellar or oligolamellar layer, said monolamellar or oligolamellar layer: (1) at least one nonionic lipophilic surfactant, (2). It comprises at least one nonionic hydrophilic surfactant and (3) at least one ionic surfactant, the microspheres having an average particle size of less than 800 nanometers.

Other Ingredients In general, when the molecule disclosed in the formula 1 is used in the formulation, the formulation may also contain other ingredients. These ingredients include, but are not limited to (this is a non-exhaustive and non-mutually exclusive list) wetting agents, spreading agents, fixing agents, penetrants, buffers, sequestrants, drift reduction. Agents, compatibilizers, defoamers, detergents, and emulsifiers. Some ingredients are listed directly below.

A wetting agent is a substance that, when added to a liquid, increases the diffusive or penetrating power of the liquid by reducing the interfacial tension between the liquid and the surface on which it diffuses. Wetting agents are used for two main functions in pesticide formulations. It increases the rate at which the powder is wetted with water during processing and production to make a soluble liquid concentrate or suspension concentrate, and mixes the product with water in a spray tank. In the meantime, it is to reduce the wetting time of the wettable powder and improve the penetration of water into the water-dispersible granules. Examples of wetting agents used in wettable powders, suspension concentrates, and water-dispersible granule preparations include sodium lauryl sulfate, sodium dioctyl sulfosuccinate, alkylphenol ethoxylates, and fatty alcohol ethoxylates.

Dispersants are substances that adsorb on the surface of particles, help maintain the dispersed state of the particles, and prevent the particles from reaggregating. The dispersant is added to the pesticide formulation to facilitate dispersion and suspension during production and to ensure that the particles are redispersed in water in the spray tank. Dispersants are widely used in wettable powders, suspension concentrates, and water-dispersible granules. Surfactants used as dispersants have the ability to strongly adsorb on the particle surface and provide a charge or steric barrier to particle reaggregation. The most commonly used surfactants are anionic, nonionic, or a mixture of the two. For wettable powders, the most common dispersants are sodium lignosulfonates. For suspension concentrates, very good adsorption and stabilization can be obtained by using a polyelectrolyte (such as sodium naphthalene sulfonic acid formaldehyde condensate). Tristyrylphenol ethoxylate phosphate esters are also used. Nonionic materials such as alkylarylethylene oxide condensates and EO-PO block copolymers may also be combined with anionic materials as dispersants for suspension concentrates. In recent years, a new type of ultra-high molecular weight polymer surfactant has been developed as a dispersant. They have a very long hydrophobic "main chain" and a large number of ethylene oxide chains that form the "teeth" of the "comb" -like surfactant. Since the hydrophobic backbone has a large number of anchoring points on the particle surface, these high molecular weight polymers can impart extremely good long-term stability to the suspension concentrate. Examples of dispersants used in pesticide formulations are sodium lignosulfonates, sodium naphthalene sulfonic acid formaldehyde condensates, tristyrylphenol ethoxylate phosphate esters, fatty alcohol ethoxylates, alkyl ethoxylates, EO-PO blocks. There are copolymers and graft copolymers.

An emulsifier is a substance that stabilizes the suspension of droplets in one liquid phase in another liquid phase. Without the emulsifier, the two liquids would separate into two immiscible liquid phases. The most commonly used emulsifier blends contain alkylphenols or fatty alcohols with 12 or more ethylene oxide units and oil-soluble calcium salts of dodecylbenzenesulfonic acid. A hydrophilic-lipophilic balance (“HLB”) value in the range of 8-18 will usually give a good stable emulsion. The stability of the emulsion may be improved by adding a small amount of EO-PO block copolymer surfactant.

The solubilizer is a surfactant that forms micelles in water at a concentration that exceeds the critical micelle concentration. In addition, the micelles can dissolve or solubilize water-insoluble substances inside the hydrophobic portion of the micelles. The types of surfactants commonly used for solubilization are nonionic substances, sorbitan monooleates, sorbitan monooleate ethoxylates, and methyloleate esters.

Surfactants may be used alone or in combination with other additives such as mineral oils or vegetable oils as an adjunct to the spray tank mixture to improve the biological performance of the pesticide against the target. The type of surfactant used for bioenhancement generally depends on the nature and mechanism of action of the pesticide. However, these are often nonionic substances such as alkyl ethoxylates, linear aliphatic alcohol ethoxylates, aliphatic amine ethoxylates and the like.

Carriers or diluents in agricultural formulations are substances that are added to pesticides to obtain products with the required strength. Carriers are usually substances with high absorption capacity, whereas diluents are usually substances with low absorption capacity. The carrier and diluent are used in the preparation of powders, wettable powders, granules and water-dispersible granules.

Organic solvents are mainly used in the formulations of emulsions, oil-in-water emulsions, suspo emulsions, and micro-formulations, and to a lesser extent in granule formulations. A mixture of solvents may also be used. The first major group of solvents are aliphatic paraffinic oils such as kerosene or refined paraffins. The second major group (and the most common) includes aromatic solvents such as xylene and higher molecular weight fractions of C9 and C10 aromatic solvents. Chlorinated hydrocarbons are useful as co-solvents to prevent the crystallization of pesticides when emulsifying the formulation into water. Alcohols may also be used as co-solvents to increase solvent power. Other solvents may include vegetable oils, seed oils, and esters of vegetable oils and seed oils.

Thickeners or gelling agents are suspension concentrates, emulsions, and saspo to alter the leology or flow properties of the liquid and to prevent the separation and sedimentation of dispersed particles or droplets. Mainly used in emulsion dosage forms. Thickeners, gelling agents and anti-sediment agents are generally divided into two categories: water-insoluble particulates and water-soluble polymers. It is possible to make a suspension concentrate formulation using clay and silica. Examples of these types of substances include, but are not limited to, montmorillonite, bentonite, magnesium aluminum silicate, and attapulsite. Water-soluble polysaccharides have been used for many years as thickening gelling agents. The most commonly used types of polysaccharides are natural extracts of seeds and seaweeds, or synthetic derivatives of cellulose. Examples of these species of substances include, but are not limited to, guar gum, locust bean gum, carrageenan, alginates, methyl cellulose, sodium carboxymethyl cellulose (SCMC), hydroxyethyl cellulose (HEC). Other types of anti-settlement agents are based on modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide. Another excellent anti-settling agent is xanthan gum.

Microorganisms can cause spoilage of formulated products. Therefore, preservatives are used to eliminate or reduce its effects. Examples of such agents include, but are not limited to, propionic acid and its sodium salt, sorbic acid and its sodium or potassium salt, benzoic acid and its sodium salt, sodium p-hydroxybenzoate, methyl p-hydroxybenzoate, and 1,2-benzoisothiazolin-3-one (BIT) can be mentioned.

Due to the presence of the surfactant, foaming of the aqueous formulation often occurs during the mixing operation through the spray tank during manufacturing and application. Defoamers are often added during the manufacturing process or before filling the bottle to reduce the tendency to foam. Generally, there are two types of antifoaming agents, namely silicones and non-silicones. Silicones are usually aqueous emulsions of dimethylpolysiloxane, whereas non-silicone defoamers are water-insoluble oils such as octanol and nonanol, or silica. In both cases, the function of the defoamer is to move the surfactant off the air-water interface.

"Environmentally friendly" agents (eg, adjuncts, surfactants, solvents) can reduce the total environmental footprint of crop protective formulations. Environmentally friendly agents are biodegradable and are generally derived from natural and / or sustainable resources such as plant and animal resources. Specific examples include vegetable oils, seed oils, and esters thereof, as well as alkoxylated alkyl polyglucosides.

The molecule of application formula 1 can be applied to any region. Specific crop areas to which such molecules apply include alfalfa, almonds, apples, barley, beans, canolas, corn, cotton, cruciferous plants, lettuce, embuck, orange, pear, pepper, potato, rice, sorghum, Includes where soybeans, strawberries, sugar cane, sorghum, sunflowers, tobacco, tomatoes, wheat, and other beneficial crops grow, or where their seeds are planted.

The molecule of formula 1 can also be applied to regions where plants such as crops are grown and where pests that can cause commercial damage to such plants are low (including non-existent). By applying such molecules to the region, the plants cultivated within the region will benefit. These benefits include, but are not limited to, assisting the good root system development of the plant, assisting the good tolerance of the plant to high-load growth conditions, improving the health of the plant, improving the yield of the plant (eg, increasing biomass and / or). Increased active ingredient content), increased plant vitality (eg increased plant growth and / or greener leaves), improved plant quality (eg increased content or composition of certain ingredients), And the increased resistance of plants to abiotic and / or biological stress can be mentioned.

When growing a variety of plants, the molecule of formula 1 can be applied with ammonium sulphate, which may bring additional benefits.

The molecule of formula 1 can be applied on, in, or around a plant genetically modified to express a unique trait. The unique trait is, for example, Bacillus thuringiensis or other insecticidal toxin, or one that develops herbicide resistance, or an insecticidal toxin, herbicide resistance, nutritional enhancement, or any For example, those having "stacked" foreign genes that express other beneficial traits.

Molecules of formula 1 may be applied to the leaves and / or fruits of plants to control pests. These molecules will come into direct contact with the pest, or will ingest such molecules when the pest eats the plant or while sucking up the sap from the plant.

The molecule of formula 1 can also be applied to soil, and when applied in this way, can control pests that feed on roots and stems. By absorbing such molecules and transporting them to the leaves of the plant, the roots can control the above-ground biting pests and sap-eating pests.

Utilizing the systemic transfer of pesticides in plants, pests can be controlled in other parts of the plant by applying the molecule of formula 1 to one part of the plant (eg, by spraying on one area). .. For example, control of leaf-eating insects is achieved by treating the soil by trickle irrigation or furrow application (eg, soil irrigation before or after planting), or by treating plant seeds before planting. obtain.

The molecule of formula 1 can be used with the bait agent. Generally with respect to bait agents, the bait agent is placed, for example, in the ground where termites can come into contact with the bait agent and / or be attracted to the bait agent. The bait may also be applied, for example, to building surfaces (horizontal, vertical, or oblique) where ants, termites, cockroaches, and flies can come into contact with the bait and / or be attracted to the bait. can.

The molecule of formula 1 can be encapsulated inside the capsule or placed on the surface of the capsule. Capsule sizes can range from nanometer size (about 100 nanometers to 900 nanometers in diameter) to micrometer size (about 10 micrometer to 900 micrometer in diameter).

The molecule of formula 1 can be applied to pest eggs. Due to the unique ability of some pest eggs to resist certain pesticides, it may be desirable to repeatedly apply such molecules to control newly emerging larvae.

The molecule of formula 1 can be applied as a seed treatment agent. Seed treatment can be applied to all types of seeds, including seeds from which plants genetically modified to express unique traits germinate. Typical examples include proteins that are toxic to invertebrate pests, such as those expressing Bacillus turgingensis or other insecticidal toxins, "Roundup Ready" seeds, etc. Those that express herbicide resistance, or those that have "stacked" exogenous genes that express pesticide toxins, herbicide resistance, nutritional enhancement, drought tolerance, or any other beneficial traits, etc. Can be mentioned. Furthermore, such seed treatment with the molecule of formula 1 can further enhance the ability of the plant to withstand high load growing conditions well. The result is a healthier and more vibrant plant, which can lead to higher yields at harvest. In general, it is predicted that about 1 gram to about 500 grams of molecules, such as about 1 gram to about 500 grams per 100,000 seeds, will give good benefits, and about 10 to about 100 grams per 100,000 seeds will give better benefits. Is expected to be obtained, with an amount of about 25 to about 75 grams per 100,000 seeds, which is expected to provide even greater benefits.

The molecule of formula 1 can be applied with one or more active ingredients in soil recovery.

The molecule of formula 1 can be used to control endoparasites and ectoparasites in the veterinary department or in the field of non-human animal rearing. Such molecules are delivered by oral administration in the form of, for example, tablets, capsules, drinks, granules, etc., by skin application in the form of, for example, immersion, spraying, infusion, spot-on, and powdering, and in the form of, for example, injection. It can be applied by parenteral administration.

Molecules of formula 1 can also be used favorably in livestock breeding, such as cattle, sheep, pigs, chickens, salmon, and geese. These molecules can also be used advantageously in pets such as horses, dogs, and cats. Certain pests to be controlled will be fleas and ticks that are annoying to such animals. Suitable formulations are administered orally to animals with drinking water or feed. Appropriate doses and formulations vary from species to species.

The molecule of formula 1 can also be used to control parasites, especially intestinal parasites, in the animals listed above.

The molecule of formula 1 can also be used in therapeutic methods for human health care. Such methods include, but are limited to, oral administration in the form of tablets, capsules, drinks, granules and the like, and skin application.

In addition, the molecule of formula 1 can also be applied to invading pests. Pests around the world are migrating to new environments (for such pests) and, after migration, become new invasive species in these new environments. Such molecules can be used for these new invasive species to control invasive species in such new environments.

In light of the above and the tables in the Table section, the following items are provided.

式中：
（Ａ） Ｒ^１、Ｒ^５、Ｒ^６、Ｒ^１１、およびＲ^１２は各々独立してＨ、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、（Ｃ_１−Ｃ_４）アルキル、（Ｃ_１−Ｃ_４）ハロアルキル、（Ｃ_１−Ｃ_４）アルコキシ、および（Ｃ_１−Ｃ_４）ハロアルコキシからなる群から選択され、
好ましくは、Ｒ^１、Ｒ^５、Ｒ^６、Ｒ^１１、およびＲ^１２は、Ｈである；
（Ｂ） Ｒ^２、Ｒ^３、及びＲ^４は、各々独立してＨ、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、（Ｃ_１〜Ｃ_４）アルキル、（Ｃ_２〜Ｃ_４）アルケニル、（Ｃ_２〜Ｃ_４）アルキニル、（Ｃ_１〜Ｃ_４）ハロアルキル、（Ｃ_１〜Ｃ_４）アルコキシ、及び（Ｃ_１〜Ｃ_４）ハロアルコキシからなる群から選択され、
好ましくは、Ｒ^２は、Ｃｌ、ＢｒまたはＣＨ_３からなる群から選択され、Ｒ^３は、Ｆ、Ｃｌ、ＢｒまたはＣＨ＝ＣＨ_２からなる群から選択され、およびＲ^４はＣｌ、ＢｒまたはＣＨ_３ からなる群から選択され、
よりさらに好ましくは、Ｒ^２、Ｒ^３、およびＲ^４はＣｌである；
（Ｃ） Ｒ^７は、（Ｃ_１−Ｃ_６）ハロアルキルであり、
好ましくはＲ^７はＣＦ_３またはＣＦ_２ＣＨ_３である；
（Ｄ） Ｒ^９は、（Ｆ）、Ｈ、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、（Ｃ_１〜Ｃ_４）アルキル、（Ｃ_１〜Ｃ_４）ハロアルキル、（Ｃ_１〜Ｃ_４）アルコキシ、及び（Ｃ_１〜Ｃ_４）ハロアルコキシからなる群から選択され、
好ましくは、Ｒ^９はＨである；
（Ｅ） Ｒ^１０は、（Ｆ）、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、（Ｃ_１〜Ｃ_４）アルキル、（Ｃ_２〜Ｃ_４）アルケニル、（Ｃ_２〜Ｃ_４）アルキニル、（Ｃ_１〜Ｃ_４）ハロアルキル、（Ｃ_１〜Ｃ_４）アルコキシ、及び（Ｃ_１〜Ｃ_４）ハロアルコキシからなる群から選択され、
好ましくは、Ｒ^１０は、Ｃｌ、Ｂｒ、Ｉ、ＣＨ_３、またはＣＦ_３である；
（Ｆ） Ｒ^９及びＲ^１０は共に、３員〜５員の飽和または不飽和のヒドロカルビル環を任意で形成することができ、
当該ヒドロカルビル環は、Ｆ、Ｃｌ、Ｂｒ、Ｉ、及びＣＮからなる群から独立して選択される１つ以上の置換基で任意選択的に置換されてもよい；
（Ｇ） Ｒ^１３およびＲ^１４は、各々独立してＨ、（Ｃ_１−Ｃ_４）アルキル、（Ｃ_２−Ｃ_４）アルケニル、（Ｃ_１−Ｃ_４）ハロアルキル、（Ｃ_１−Ｃ_４）アルコキシ、および（Ｃ_１−Ｃ_４）ハロアルコキシからなる群から選択され、
好ましくは、Ｒ^１３またはＲ^１４は、ＣＨ_３である；
（Ｈ） Ｘは、Ｃ、ＳおよびＰ（Ｃ_１〜Ｃ_６）アルキルからなる群から選択され、
好ましくは、Ｘは、ＣまたはＳである；
（Ｉ） ｎは、１または２である；
（Ｊ） Ｒ^１５は、（Ｃ_１−Ｃ_４）アルキル、（Ｃ_２−Ｃ_４）アルケニル、（Ｃ_１−Ｃ_４）ハロアルキル、（Ｃ_１−Ｃ_４）アルコキシ、（Ｃ_１−Ｃ_４）ハロアルコキシ、フェニル、およびＮＨ（Ｃ_１−Ｃ_４）ハロアルキルからなる群から選択され、
式中、アルキル、アルケニル、ハロアルキル、アルコキシ、ハロアルコキシ、およびフェニルの各々は、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、およびＯＨからなる群から独立して選択される１個以上の置換基で任意で置換されてもよく、
好ましくは、Ｒ^１５は、ＣＨ_２ＣＨ_２ＣＦ_３またはＮＨＣＨ_２ＣＦ_３である、を有する分子；ならびに
式１の分子の農学的に許容可能な酸付加塩、塩誘導体、溶媒和物、エステル誘導体、結晶多形体、同位体、分割立体異性体、および互変異性体。
２．式中、
（Ａ） Ｒ^１、Ｒ^５、Ｒ^６、Ｒ^１１、およびＲ^１２はＨである；
（Ｂ） Ｒ^２、Ｒ^３、およびＲ^４は各々独立してＨ、Ｆ、Ｃｌ、Ｂｒ、Ｉ、（Ｃ_１−Ｃ_４）アルキル、（Ｃ_２−Ｃ_４）アルケニル、および（Ｃ_１−Ｃ_４）ハロアルキルからなる群から選択される；
（Ｃ） Ｒ^７は、（Ｃ_１−Ｃ_６）ハロアルキルである；
（Ｄ） Ｒ^９は、Ｈである；
（Ｅ） Ｒ^１０は、Ｈ、Ｆ、Ｃｌ、Ｂｒ、Ｉ、（Ｃ_１〜Ｃ_４）アルキル、及び（Ｃ_１〜Ｃ_４）ハロアルキルからなる群から選択される；
（Ｇ） Ｒ^１３およびＲ^１４は各々独立してＨおよび（Ｃ_１−Ｃ_４）アルキルからなる群から選択される；
（Ｈ） Ｘは、ＣとＳからなる群から選択される；
（Ｉ） ｎは、１または２である；および
（Ｊ） Ｒ^１５は、（Ｃ_１〜Ｃ_４）ハロアルキルおよびＮＨ（Ｃ_１〜Ｃ_４）ハロアルキルからなる群から選択される、１に記載の分子。
３．当該分子が表２の分子のうちの１つからなる群から選択される、１に記載の分子。
４．当該分子が表１の分子のうちの１つからなる群から選択される、１に記載の分子。
５．１つ以上の活性成分をさらに含む、１、２、３、または４のうちのいずれか１つに記載の分子を含む農薬組成物。
６．当該活性成分がＡＩＧＡからのものである、５に記載の農薬組成物。
７．当該活性成分がＡＩ−１、１，３−ジクロロプロペン、クロルピリホス、クロルピリホス−メチル、ヘキサフルムロン、メトキシフェノジド、ノビフルムロン、スピネトラム、スピノサド、スルホキサフロル、及びフッ化スルフリルからなる群から選択される、５に記載の農薬組成物。
８．ＭｏＡ物質をさらに含む、１、２、３、または４のうちのいずれか１つに記載の分子を含む農薬組成物。
９．当該ＭｏＡ物質がＭｏＡＭＧＡからのものである、７に記載の農薬組成物。
１０．式１に記載される分子と当該活性成分との重量比が表Ｂから選択される、５、６、７、８、または９のいずれか１つに記載の農薬組成物。
１１．害虫を防除するプロセスであって、当該プロセスが、ある場所に農薬的に有効な量の１、２、３、４のいずれか１つに記載の分子を適用することを含む、プロセス。
１２．害虫を防除するプロセスであって、当該プロセスが、ある場所に農薬的に有効な量の５、６、７、８、９、または１０のうちのいずれか１つに記載の農薬組成物を適用することを含む、プロセス。
１３．当該分子が農学的に許容可能な酸付加塩の形態である、１、２、３、もしくは４のいずれか１つに記載の分子、または５、６、７、８、９、もしくは１０のいずれか１つに記載の農薬組成物。
１４．当該分子が塩誘導体の形態である、１、２、３、もしくは４のうちのいずれか１つに記載の分子、または５、６、７、８、９、もしくは１０のうちのいずれか１つに記載の農薬組成物。
１５．当該分子が溶媒和物の形態である、１、２、３、もしくは４のうちのいずれか１つに記載の分子、または５、６、７、８、９、もしくは１０のうちのいずれか１つに記載の農薬組成物。
１６．当該分子がエステル誘導体の形態である、１、２、３、もしくは４のうちのいずれか１つに記載の分子、または５、６、７、８、９、もしくは１０のうちのいずれか１つに記載の農薬組成物。
１７．当該分子が結晶多形体の形態である、１、２、３、もしくは４のうちのいずれか１つに記載の分子、または５、６、７、８、９、もしくは１０のうちのいずれか１つに記載の農薬組成物。
１８．当該分子が重水素、三重水素、および／または^１４Ｃを有する、１、２、３、もしくは４のうちのいずれか１つに記載の分子、または５、６、７、８、９、もしくは１０のうちのいずれか１つに記載の農薬組成物。
１９．当該分子が１つ以上の立体異性体の形態である、１、２、３、もしくは４のうちのいずれか１つに記載の分子、または５、６、７、８、９、もしくは１０のうちのいずれか１つに記載の農薬組成物。
２０．当該分子が分割立体異性体の形態である、１、２、３、もしくは４のうちのいずれか１つに記載の分子、または５、６、７、８、９、もしくは１０のうちのいずれか１つに記載の農薬組成物。
２１．当該農薬組成物が別の活性成分をさらに含む、５、６、７、８、９、または１０のうちのいずれか１つに記載の農薬組成物。
２２．当該農薬組成物が２つ以上の活性成分をさらに含む、５、６、７、８、９、または１０のうちのいずれか１つに記載の農薬組成物。
２３．当該活性成分が式１の当該分子のＭｏＡとは異なるＭＯＡを有する、５、６、７、８、９、または１０のうちのいずれか１つに記載の農薬組成物。
２４．当該農薬組成物が、殺ダニ特性、殺藻特性、殺鳥特性、殺菌特性、殺真菌特性、除草特性、殺虫特性、軟体動物駆除特性、殺線虫特性、殺鼠特性、及び／または殺ウイルス特性を有する活性成分を含む、５、６、７、８、９、または１０のうちのいずれか１つに記載の農薬組成物。
２５．当該農薬組成物が、摂食阻害剤、鳥忌避剤、化学不妊剤、除草剤毒性緩和剤、昆虫誘引剤、昆虫忌避剤、哺乳動物忌避剤、交尾阻害剤、植物活性剤、植物成長調節剤、及び／または相乗剤である活性成分を含む、５、６、７、８、９、または１０のうちのいずれか１つに記載の農薬組成物。
２６．当該農薬組成物がバイオ農薬である活性成分を含む、５、６、７、８、９、または１０のうちのいずれか１つに記載の農薬組成物。
２７．式１の分子と活性成分との当該重量比が１００：１〜１：１００である、５、６、７、８、９、または１０のうちのいずれか１つに記載の農薬組成物。
２８．式１の分子と活性成分との当該重量比が５０：１〜１：５０である、５、６、７、８、９、または１０のうちのいずれか１つに記載の農薬組成物。
２９．式１の分子と活性成分との当該重量比が２０：１〜１：２０である、５、６、７、８、９、または１０のうちのいずれか１つに記載の農薬組成物。
３０．式１の分子と活性成分との当該重量比が１０：１〜１：１０である、５、６、７、８、９、または１０のうちのいずれか１つに記載の農薬組成物。
３１．式１の分子と活性成分との当該重量比が５：１〜１：５である、５、６、７、８、９、または１０のうちのいずれか１つに記載の農薬組成物。
３２．式１の分子と活性成分との当該重量比が３：１〜１：３である、５、６、７、８、９、または１０のうちのいずれか１つに記載の農薬組成物。
３３．式１の分子と活性成分との当該重量比が２：１〜１：２である、５、６、７、８、９、または１０のうちのいずれか１つに記載の農薬組成物。
３４．式１の分子と活性成分との当該重量比が１：１である、５、６、７、８、９、または１０のうちのいずれか１つに記載の農薬組成物。
３５．式１の分子と活性成分との当該重量比がＸ：Ｙとして示され、ここでＸは式１の分子の重量部であり、Ｙは活性成分の重量部であり、さらに、Ｘの重量部の数値範囲が０＜ｘ≦１００であり、Ｙの重量部の数値範囲が０＜Ｙ≦１００であり、さらに、Ｘ及びＹが表Ｃから選択される、５、６、７、８、９、または１０のうちのいずれか１つに記載の農薬組成物。
３６．式１の分子と活性成分との重量比の範囲が、Ｘ_１：Ｙ_１〜Ｘ_２：Ｙ_２として示され、さらに、Ｘ_１＞Ｙ_１かつＸ_２＜Ｙ_２である、３５に記載の農薬組成物。
３７．式１の分子と活性成分との重量比の範囲が、Ｘ_１：Ｙ_１〜Ｘ_２：Ｙ_２として示され、さらに、Ｘ_１＞Ｙ_１かつＸ_２＞Ｙ_２である、３５に記載の農薬組成物。
３８．式１の分子と活性成分との重量比の範囲が、Ｘ_１：Ｙ_１〜Ｘ_２：Ｙ_２として示され、さらに、Ｘ_１＜Ｙ_１かつＸ_２＜Ｙ_２である、３５に記載の農薬組成物。
３９．当該組成物が相乗剤である、３５に記載の農薬組成物。
４０．当該害虫が節足動物門からのものである、１２に記載のプロセス。
４１．当該害虫が軟体動物門からのものである、１２に記載のプロセス。
４２．当該害虫が線形動物門からのものである、１２に記載のプロセス。
４３．当該害虫が、
アリ、アブラムシ、甲虫、シミ、ゴキブリ、コオロギ、ハサミムシ、ノミ、ハエ、バッタ、ヨコバイ、シラミ（フナムシを含む）、イナゴ、ダニ、ガ、線虫、カイガラムシ、コムカデ、シロアリ、アザミウマ、マダニ、スズメバチ、及び／またはコナジラミである、１２に記載のプロセス。
４４．当該場所が、アルファルファ、アーモンド、リンゴ、オオムギ、マメ、カノーラ、トウモロコシ、ワタ、アブラナ科植物、レタス、オート麦、オレンジ、ナシ、コショウ、ジャガイモ、コメ、モロコシ、ダイズ、イチゴ、サトウキビ、テンサイ、ヒマワリ、タバコ、トマト、コムギ、及びその他の貴重な作物が成長する場所、またはそれらの種子が植えられる場所である、１２に記載のプロセス。
４５．当該農薬組成物が硫酸アンモニウムをさらに含む、５、６、７、８、９、または１０のうちのいずれか１つに記載の農薬組成物。
４６．当該場所が、固有の形質を発現するように遺伝子組み換えされた植物が植えられる場所である、１２に記載のプロセス。
４７．当該適用が、植物の葉及び／または果実部に対して行われる、１２に記載のプロセス。
４８．当該適用が土壌に対して行われる、１２に記載のプロセス。
４９．当該適用が、細流灌漑、畝間適用、または植え付け前もしくは後の土壌灌注によって行われる、１２に記載のプロセス。
５０．当該適用が、植物の葉及び／もしくは果実部に対して、または植え付け前に植物の種子を処理することによって行われる、１２に記載のプロセス。
５１．１、２、３、または４のうちのいずれか１つに記載の分子、および種子を含む農薬組成物。
５２．１、２、３、もしくは４に記載の分子、または５、６、７、８、９、もしくは１０に記載の農薬組成物を、種子に適用することを含むプロセス。
５３．１、２、３、または４のいずれか１つに記載の分子を、内部寄生虫及び／または外部寄生虫を防除するために非ヒト動物を含む場所に適用することを含むプロセス。
５４．農薬組成物を製造するためのプロセスであって、当該プロセスが、１、２、３、または４のうちのいずれか１つに記載の分子と、１つ以上の活性成分とを混合することを含む、プロセス。 1. 1. The following formula

During the ceremony:
(A) R ¹ , R ⁵ , R ⁶ , R ¹¹ and R ¹² are independently H, F, Cl, Br, I, CN, (C _1- C ₄ ) alkyl, (C _1- C _4). ) _haloalkyl, is selected from _(C 1 -C ₄₎ alkoxy, and _(C 1 -C ₄₎ group consisting of haloalkoxy,
Preferably, R ¹ , R ⁵ , R ⁶ , R ¹¹ and R ¹² are H;
^{(B) R 2, R 3} , and ^{R 4} are each independently H, F, Cl, Br, I, CN, (C 1 ~C 4) _{alkyl, (C} 2 _{~C 4)} alkenyl, (C Selected from the group consisting of _{2 to} C ₄ ) alkynyl, (C _{1 to} C ₄ ) haloalkyl, (C _{1 to} C ₄ ) alkoxy, and (C _{1 to} C _{4) haloalkoxy.}
Preferably, R ² is selected from the group consisting of Cl, Br or CH ₃ ^{, R 3} is selected from the group consisting of F, Cl, Br or CH = CH ₂ ^{, and R 4} is selected from the group consisting of Cl, Br or CH. Selected from a group of ₃
Even more preferably, R ² , R ³ , and R ⁴ are Cl;
(C) R ⁷ is (C _1- C ₆ ) haloalkyl and
Preferably R ⁷ is CF ₃ or CF ₂ CH ₃ ;
(D) R ⁹ is (F), H, F, Cl, Br, I, CN, (C _{1 to} C ₄ ) alkyl, (C _{1 to} C ₄ ) haloalkyl, (C _{1 to} C ₄ ) alkoxy, And (C _{1 to} C ₄ ) selected from the group consisting of haloalkoxy,
Preferably, R ⁹ is H;
^{(E) R 10} is, (F), F, Cl , Br, I, CN, (C 1 ~C 4) _{alkyl, (C} 2 _{~C 4) alkenyl, (C} 2 _{~C 4)} alkynyl, (C Selected from the group consisting of _{1 to} C ₄ ) haloalkyl, (C _{1 to} C ₄ ) alkoxy, and (C _{1 to} C _{4) haloalkoxy.}
Preferably, R ¹⁰ is Cl, Br, I, CH ₃ , or CF ₃ ;
(F) Both R ⁹ and R ¹⁰ can optionally form a 3- to 5-membered saturated or unsaturated hydrocarbyl ring.
The hydrocarbyl ring may be optionally substituted with one or more substituents independently selected from the group consisting of F, Cl, Br, I, and CN;
^{(G) R 13} and ^{R 14} are each independently _{H, (C} 1 -C _{4) alkyl, (C} 2 -C _{4) alkenyl, (C} 1 -C _{4) haloalkyl,} (C 1 _-C 4) alkoxy, and _(C 1 -C ₄₎ is selected from the group consisting of haloalkoxy,
Preferably R ¹³ or R ¹⁴ is CH ₃ ;
(H) X is selected from the group consisting of C, S and P (C _1- C _{6) alkyl.}
Preferably X is C or S;
(I) n is 1 or 2;
(J) R ¹⁵ is (C _1- C ₄ ) alkyl, (C _2- C ₄ ) alkenyl, (C _1- C ₄ ) haloalkyl, (C _1- C ₄ ) alkoxy, (C _1- C ₄ ). haloalkoxy, phenyl, and NH _(C 1 -C ₄₎ is selected from the group consisting of haloalkyl,
In the formula, each of alkyl, alkenyl, haloalkyl, alkoxy, haloalkoxy, and phenyl is optional with one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, and OH. May be replaced with
Preferably, R ¹⁵ is _{a molecule having CH 2} CH ₂ CF ₃ or NHCH ₂ CF ₃ ; as well as an agriculturally acceptable acid addition salt, salt derivative, solvate, ester derivative of the molecule of formula 1. , Crystal polymorphs, isotopes, split steric isomers, and tautomers.
2. During the ceremony
(A) R ¹ , R ⁵ , R ⁶ , R ¹¹ and R ¹² are H;
(B) R ² , R ³ , and R ⁴ are independently H, F, Cl, Br, I, (C _1- C ₄ ) alkyl, (C _2- C ₄ ) alkenyl, and (C _{1-), respectively.} C ₄ ) Selected from the group consisting of haloalkyl;
(C) R ⁷ is (C _1- C ₆ ) haloalkyl;
(D) R ⁹ is H;
^{(E) R 10} is, H, F, Cl, Br, _I, is selected from the group consisting of _(C 1 _{~C 4)} alkyl, and _(C 1 _{~C 4)} haloalkyl;
^{(G) R 13} and ^{R 14} H and each independently is _(C 1 -C ₄₎ is selected from the group consisting of alkyl;
(H) X is selected from the group consisting of C and S;
(I) n is 1 or 2; and (J) R ¹⁵ is selected from the group consisting of (C _1- C ₄ ) haloalkyl and NH (C _1- C _{4) haloalkyl according to 1.} molecule.
3. 3. The molecule according to 1, wherein the molecule is selected from the group consisting of one of the molecules in Table 2.
4. The molecule according to 1, wherein the molecule is selected from the group consisting of one of the molecules in Table 1.
5. A pesticide composition comprising the molecule according to any one of 1, 2, 3, or 4, further comprising one or more active ingredients.
6. 5. The pesticide composition according to 5, wherein the active ingredient is from AIGA.
7. 5. The active ingredient is selected from the group consisting of AI-1,1,3-dichloropropene, chlorpyrifos, chlorpyrifos-methyl, hexaflumron, methoxyphenozide, nobiflumron, spinetram, spinosad, sulfoxaflor, and sulfuryl fluoride. Agricultural chemical composition.
8. A pesticide composition comprising the molecule according to any one of 1, 2, 3, or 4, further comprising a MoA substance.
9. 7. The pesticide composition according to 7, wherein the MoA substance is from MoAMGA.
10. The pesticide composition according to any one of 5, 6, 7, 8 or 9, wherein the weight ratio of the molecule represented by the formula 1 to the active ingredient is selected from Table B.
11. A process for controlling pests, which comprises applying a pesticide-effective amount of a molecule according to any one of 1, 2, 3, and 4 to a location.
12. A process of controlling pests, wherein the process applies a pesticide-effective amount of the pesticide composition according to any one of 5, 6, 7, 8, 9, or 10 to a location. A process that involves doing.
13. The molecule according to any one of 1, 2, 3, or 4 or any of 5, 6, 7, 8, 9, or 10 in which the molecule is in the form of an agronomically acceptable acid addition salt. The pesticide composition according to one.
14. The molecule according to any one of 1, 2, 3, or 4 in which the molecule is in the form of a salt derivative, or any one of 5, 6, 7, 8, 9, or 10. Agricultural chemical composition according to.
15. The molecule according to any one of 1, 2, 3, or 4 in which the molecule is in the form of a solvate, or any one of 5, 6, 7, 8, 9, or 10. The pesticide composition according to one.
16. The molecule according to any one of 1, 2, 3, or 4 in which the molecule is in the form of an ester derivative, or any one of 5, 6, 7, 8, 9, or 10. Agricultural chemical composition according to.
17. The molecule according to any one of 1, 2, 3, or 4 in which the molecule is in the form of a crystalline polymorph, or any one of 5, 6, 7, 8, 9, or 10. The pesticide composition according to one.
18. The molecule according to any one of 1, 2, 3, or 4, or 5, 6, 7, 8, 9, or 10 in which the molecule has deuterium, tritium, and / or ^{14 C.} The pesticide composition according to any one of.
19. The molecule according to any one of 1, 2, 3, or 4 in which the molecule is in the form of one or more stereoisomers, or of 5, 6, 7, 8, 9, or 10. The pesticide composition according to any one of the above.
20. The molecule according to any one of 1, 2, 3, or 4 in which the molecule is in the form of a split stereoisomer, or any of 5, 6, 7, 8, 9, or 10. The pesticide composition according to one.
21. The pesticide composition according to any one of 5, 6, 7, 8, 9, or 10, wherein the pesticide composition further comprises another active ingredient.
22. The pesticide composition according to any one of 5, 6, 7, 8, 9, or 10, wherein the pesticide composition further comprises two or more active ingredients.
23. The pesticide composition according to any one of 5, 6, 7, 8, 9, or 10, wherein the active ingredient has a MOA different from that of the molecule of the formula 1.
24. The pesticide composition has acaricidal properties, algae-killing properties, bird-killing properties, fungicidal properties, fungicidal properties, herbicidal properties, insecticidal properties, mollusk extermination properties, nematode-killing properties, rodent-killing properties, and / or virus-killing properties. The pesticide composition according to any one of 5, 6, 7, 8, 9, or 10, which comprises an active ingredient having properties.
25. The pesticide composition is a feeding inhibitor, avian repellent, a chemical fertility agent, a herbicide toxicity palliative, an insect attractant, an insect repellent, a mammalian repellent, a mating inhibitor, a plant activator, a plant growth regulator. , And / or the pesticide composition according to any one of 5, 6, 7, 8, 9, or 10 containing an active ingredient that is a synergistic agent.
26. The pesticide composition according to any one of 5, 6, 7, 8, 9, or 10, wherein the pesticide composition contains an active ingredient that is a biopesticide.
27. The pesticide composition according to any one of 5, 6, 7, 8, 9, or 10, wherein the weight ratio of the molecule of the formula 1 to the active ingredient is 100: 1 to 1: 100.
28. The pesticide composition according to any one of 5, 6, 7, 8, 9, or 10, wherein the weight ratio of the molecule of the formula 1 to the active ingredient is 50: 1 to 1:50.
29. The pesticide composition according to any one of 5, 6, 7, 8, 9, or 10, wherein the weight ratio of the molecule of the formula 1 to the active ingredient is 20: 1 to 1:20.
30. The pesticide composition according to any one of 5, 6, 7, 8, 9, or 10, wherein the weight ratio of the molecule of the formula 1 to the active ingredient is 10: 1 to 1:10.
31. The pesticide composition according to any one of 5, 6, 7, 8, 9, or 10, wherein the weight ratio of the molecule of the formula 1 to the active ingredient is 5: 1 to 1: 5.
32. The pesticide composition according to any one of 5, 6, 7, 8, 9, or 10, wherein the weight ratio of the molecule of the formula 1 to the active ingredient is 3: 1 to 1: 3.
33. The pesticide composition according to any one of 5, 6, 7, 8, 9, or 10, wherein the weight ratio of the molecule of the formula 1 to the active ingredient is 2: 1 to 1: 2.
34. The pesticide composition according to any one of 5, 6, 7, 8, 9, or 10, wherein the weight ratio of the molecule of the formula 1 to the active ingredient is 1: 1.
35. The weight ratio of the molecule of formula 1 to the active ingredient is shown as X: Y, where X is the weight portion of the molecule of formula 1, Y is the weight portion of the active ingredient, and further, the weight portion of X. The numerical range of is 0 <x ≦ 100, the numerical range of the weight part of Y is 0 <Y ≦ 100, and X and Y are selected from Table C 5, 6, 7, 8, 9 , Or the pesticide composition according to any one of 10.
36. 35, wherein the range of weight ratios of the molecule of formula 1 to the active ingredient is _{shown as X 1} : Y _{1 to} X ₂ : Y ₂ , and X ₁ > Y ₁ and X ₂ <Y _2. Agricultural chemical composition.
37. 35, wherein the range of weight ratios of the molecule of formula 1 to the active ingredient is _{shown as X 1} : Y _{1 to} X ₂ : Y ₂ , and further X ₁ > Y ₁ and X ₂ > Y _2. Agricultural chemical composition.
38. The range of the weight ratio of the molecule of the formula 1 to the active ingredient is _{shown as X 1} : Y _{1 to} X ₂ : Y ₂ , and further described in 35 _{, where X 1} <Y ₁ and X ₂ <Y _2. Agricultural chemical composition.
39. 35. The pesticide composition according to 35, wherein the composition is a synergistic agent.
40. 12. The process according to 12, wherein the pest is from the phylum Arthropod.
41. 12. The process according to 12, wherein the pest is from the phylum Mollusc.
42. 12. The process according to 12, wherein the pest is from the phylum C. elegans.
43. The pest
Ants, aphids, beetles, stains, cockroaches, crickets, grasshoppers, fleas, flies, grasshoppers, whiteflies, locusts (including fungus), locusts, mites, moths, nematodes, scale insects, komukade, termites, horse mackerel, ticks, spider bees, And / or the process according to 12, which is a whitefly.
44. The locations are alfalfa, almonds, apples, barley, beans, canolas, corn, cotton, cruciferous plants, lettuce, oats, oranges, pears, peppers, potatoes, rice, sorghum, soybeans, strawberries, sugar beets, sugar beets, sunflowers. , Tobacco, tomato, wheat, and other valuable crops grow, or where their seeds are planted, the process according to 12.
45. The pesticide composition according to any one of 5, 6, 7, 8, 9, or 10, wherein the pesticide composition further comprises ammonium sulfate.
46. 12. The process according to 12, wherein the site is where a plant genetically modified to express a unique trait is planted.
47. 12. The process according to 12, wherein the application is made to the leaves and / or fruits of the plant.
48. 12. The process according to 12, wherein the application is made to soil.
49. 12. The process according to 12, wherein the application is performed by trickle irrigation, furrow application, or soil irrigation before or after planting.
50. 12. The process according to 12, wherein the application is made to the leaves and / or fruits of the plant, or by treating the seeds of the plant prior to planting.
51. A pesticide composition comprising the molecule and seed according to any one of 2, 3, or 4.
A process comprising applying to a seed the molecule according to 52.1, 2, 3, or 4, or the pesticide composition according to 5, 6, 7, 8, 9, or 10.
A process comprising applying the molecule according to any one of 53.1, 2, 3, or 4 to a site containing a non-human animal to control endoparasites and / or ectoparasites.
54. A process for producing a pesticide composition, wherein the process mixes the molecule according to any one of 1, 2, 3, or 4 with one or more active ingredients. Including, process.

The title of this document is for convenience only and should not be used to interpret any part of this document.
Table Section Table 2 Structure and preparation method of F-based molecules

Table 3 Structure and preparation method of C-based molecule

Table 4 Analytical data on the molecules listed in Table 2

Table 5 Structure and preparation method of FC compounds

Table 6 Structure and preparation method of CC-based molecules

Table 7: Analytical data of the compounds in Table 5

Table 8 Structure and preparation method of pF-based molecule

Table 9: Analytical data for the molecules listed in Table 8

Table ABC Biological Results

Comparative Data The BAW and CL bioassays were performed according to the procedure outlined in Example A: Beet armyworm (“BAW”) and cabbage looper (“CL”) bioassays using the indicated concentrations. The results are shown in Table CD1.
Table CD1

Claims (15)

The following formula

During the ceremony:
(A) R ¹ , R ⁵ , R ⁶ , R ¹¹ and R ¹² are independently H, F, Cl, Br, I, CN, (C _1- C ₄ ) alkyl, (C _1- C _4). ) haloalkyl, from (C ₁ -C ₄₎ alkoxy, and (C ₁ -C ₄₎ group consisting of haloalkoxy;
(B) R ^2, R ³ and R ⁴ are each independently H, F, Cl, Br, I, CN, (C 1 ~C 4) alkyl, (C ₂ ~C ₄₎ alkenyl, (C ₂ Selected from the group consisting of ~ C ₄ ) alkynyl, (C ₁ ~ C ₄ ) haloalkyl, (C ₁ ~ C ₄ ) alkoxy and (C ₁ ~ C _{4) haloalkoxy;}
(C) R ⁷ is (C _1- C ₆ ) haloalkyl;
(D) R ⁹ is (F), H, F, Cl, Br, I, CN, (C _1- C ₄ ) alkyl, (C _1- C ₄ ) haloalkyl, (C _1- C ₄ ) alkoxy, And (C _1- C ₄ ) selected from the group consisting of haloalkoxy;
(E) R ¹⁰ is, (F), F, Cl , Br, I, CN, (C 1 ~C 4) alkyl, (C ₂ ~C ₄₎ alkenyl, (C ₂ ~C ₄₎ alkynyl, (C Selected from the group consisting of _{1 to} C ₄ ) haloalkyl, (C _{1 to} C ₄ ) alkoxy, and (C _{1 to} C _{4) haloalkoxy.}
(F) Both R ⁹ and R ¹⁰ can optionally form 3- to 5-membered saturated or unsaturated hydrocarbyl rings.
The hydrocarbyl ring may be optionally substituted with one or more substituents independently selected from the group consisting of F, Cl, Br, I, and CN;
(G) R ¹³ and R ¹⁴ are each independently H, (C ₁ -C ₄₎ alkyl, (C ₂ -C ₄₎ alkenyl, (C ₁ -C ₄₎ haloalkyl, (C ₁ -C ₄₎ alkoxy, and (C ₁ -C ₄₎ is selected from the group consisting of haloalkoxy;
(H) X is selected from the group consisting of C, S and P (C _1- C _{6) alkyl;}
(I) n is 1 or 2;
(J) R ¹⁵ is (C _1- C ₄ ) alkyl, (C _2- C ₄ ) alkenyl, (C _1- C ₄ ) haloalkyl, (C _1- C ₄ ) alkoxy, (C _1- C ₄ ). haloalkoxy, phenyl, and NH (C ₁ -C ₄₎ is selected from the group consisting of haloalkyl,
In the formula, each of alkyl, alkenyl, haloalkyl, alkoxy, haloalkoxy, and phenyl is optional with one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, and OH. Compounds having, which may be substituted with; as well as pharmaceutically acceptable acid addition salts, solvates, isotopes, split steric isomers, and tautomers of the compounds of formula 1. During the ceremony
(A) R ¹ , R ⁵ , R ⁶ , R ¹¹ , and R ¹² are H;
(B) R ² , R ³ , and R ⁴ are independently H, F, Cl, Br, I, (C _1- C ₄ ) alkyl, (C _2- C ₄ ) alkenyl, and (C _{1-), respectively.} C ₄ ) Selected from the group consisting of haloalkyl;
(C) R ⁷ is (C _1- C ₆ ) haloalkyl;
(D) R ⁹ is H;
(E) R ¹⁰ is selected from the group consisting of H, F, Cl, Br, I, (C _{1 to} C ₄ ) alkyl, and (C _{1 to} C _{4) haloalkyl;}
(G) R ¹³ and R ¹⁴ H and each independently is (C ₁ -C ₄₎ is selected from the group consisting of alkyl;
(H) X is selected from the group consisting of C and S;
(I) n is 1 or 2; and (J) R ¹⁵ is selected from the group consisting of (C _{1 to} C ₄ ) haloalkyl and NH (C _{1 to} C _{4) haloalkyl, claim 1.} The compound described. The compound according to claim 1, wherein the compound is selected from one of the compounds in the table below .

.. The compound according to claim 1, wherein the compound is selected from one of the compounds in the table below .

.. A pesticide composition comprising the compound according to any one of claims 1, 2, 3, or 4, further comprising one or more active ingredients. The pesticide composition according to claim 5, wherein the active ingredients are from the active ingredient group alpha (AIGA), which collectively means the following substances.
(1) (3-ethoxypropyl) mercury bromide, 1,2-dibromoethane, 1,2-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropene, 1-MCP, 1-methylcyclopropene, 1-naphthol, 2- (octylthio) ethanol, 2,3,3-TPA, 2,3,5-tri-iodobenzoic acid, 2,3,6-TBA, 2,4,5-T, 2,4 , 5-TB, 2,4,5-TP, 2,4-D, 2,4-DB, 2,4-DEB, 2,4-DEP, 2,4-DES, 2,4-DP, 2 , 4-MCPA, 2,4-MCPB, 2iP, 2-methoxymethylmercuric chloride, 2-phenylphenol, 3,4-DA, 3,4-DB, 3,4-DP, 3,6-dichloropicolinic acid, 4-Aminopyridine, 4-CPA, 4-CPB, 4-CPP, 4-Hydroxyphenyl alcohol, 8-hydroxyquinoline sulfate, 8-phenylmercuryoxyquinoline, abamectin, abamectin-aminomethyl, absicic acid, ACC, acetylate. , Acequinosyl, acetamipride, acethion, acetochlor, acetophenate, acetophos, acetoprol, acibenzoral, asifluorphen, acronifen, ACN, acrep, aclinatrin, achlorine, acrylonitrile, acipetax, afidopyropen, ahoxolana, alacrol, alanap Albendazole, aldicalve, aldicalb sulfone, aldimorph, aldoxycarb, aldrin, alesulin, alicin, allydocrol, allosamidin, aloxidim, allylalcohol, alixylve, allolac, α-cypermethrin, α-endosulfane, alphamethrin, altretamine, Aluminum Phosphate, Aluminum Phosphate, Amethcladine, Ametridione, Amethrin, Amethrine, Amibudin, Amicabazole, Amicartiazole, Amidithion, Azidoflumeth, Amidosulfuron, Aminocarb, Aminocyclopyracrol, Aminopyralid, Aminotriazol -Methyl, amiprophos, amiprophos-methyl, amisulfome, amitone, amitraz, amitrol, ammonium sulfamate, amovam, amorphous silica gel, amorphous silicon dioxide, ampropifphos, AMS, anabacin, ansimidol, anila Zin, anilophos, anislon, anthraquinone, anz, aholate, alamite, alprocarb, arsenic trioxide, asomet, aspirin, aslam, atidathion, atlaston, atlasin, aureofungin, avelmectin B1, AVG, abigricin, azaconazole, azaziractin. Azamethifos, azidithione, azisulfone, adihocetyl, azinephos-ethyl, azinephosmethyl, azinephos-methyl, adiprothrin, adiprothrin, azitiram, azobenzene, azocyclotin, azotoate, azoxystrobin, bakumedesh, balban, barbanate, barium hexafluoride , Barium polysulfide, barium silicate, baltrin, basic copper carbonate, basic copper chloride, basic copper sulphate, BCPC, beflubutamide, benaraxyl, benaraxyl-M, benazolline, bencarbazone, bencrothias, bendakingbingji, benziocarb, benzy Oxide, benefin, benfluthrin, benfracarb, benfresate, benmifangkaoan, benodanyl, benomil, benoxacol, benoxaphos, benquinox, bensulfuron, benslide, bensultap, ventallon, ventazone, ventazone, benchavaricarb , Benzadox, benzalkonium chloride, benzamacryl, benzamizole, benzamorph, benzenehexachloride, benzfendizone, benzimine, benziplum, benzobicyclon, benzoepine, benzofanap, benzofluore, benzohydroxamic acid, benzomate, benzophosphate, benzothiazole, benzo Bingiflupill, benzoximate, benzoylprop, benzthiazulone, benzokaotong, benzyl benzoate, benzyladenine, velverin, β-cyfluthrin, β-cypermethrin, betoxazine, BHC, bialaphos, bicyclopyrone, biphenazeto, biphenox, biphenthrin, Bifujunji, Vilanaphos, Vinapacryl, Bintinsiao, Bioaletrin, Bioetanomethrin, Biopermethrin, Bioresmethrin, Biphenyl, Bisazil, Bismerthiazole, Bismerthiazole-Copper, Bisphenylmercury methylenedi (x-naphthalen-y-sulfonate), Bispyribac, Bistriflulon, Bisultap, Vitel Tanol, bithionol, bixaphen, blasticidin-S, boric acid, Bordeaux solution, boric acid, boscalide, BPPS, brushnolide, brushnolide-ethyl, brevicomine, brodifacomum, brophenoplox, brofenvalerate, brofanilide, brofluthrinete, bromacil, bromazilone , Bromclophos, brometalin, bromesulin, bromfenbinphos, bromoacetamide, bromobonil, bromobutide, bromocylene, bromocyclen, bromo-DDT, bromophenoxym, bromophos, bromomwrn, bromophos, bromophos-ethyl Rate, bromotalonil, bromoxinyl, brompyrazone, bromconazole, bronopol, BRP, BTH, bucarporate, bufencarb, buminaphos, bupilimate, buprofezin, bordeaux solution, busulfan, busulfan, busulfan, butacarb, butachlor Butane-fipronil, butatiophos, butenachlor, butene-fipronil, butetrin, butidazole, butiobate, butiuron, butyphos, butocarboxym, butonate, butopyronoxyl, butoxycarboxym, butrulin, butridine, butoroxydim, butulamine, butyrate, butylchlorophos, Butylene-fipronil, cacodylate, cadeyusaphos, cafentrol, calciferol, calcium arsenate, calcium chlorate, calcium cyanamide, calcium cyanide, calcium polysulfide, carbinophos, cambendichlor, camfechlor, camphor, captahole, captan, carbam , Carbamorph, carbarolate, carbaryl, carbaryl, carbaslam, carbathione, carbendazim, carbendersol, carbetamid, carbophenothione, carbofuran, carbon disulfide, carbon tetrachloride, carbonyl sulfide, carbophenothione, carbophos, Carbosulfane, Carboxazole, Carboxido, Carboxin, Calfentrazone, Calpropamide, Cartap, Carbaryl, Carboyl, CAVP, CDAA, CDEA, CDEC, Celocidin, CEPC, Ceralle, Serenox, Sevadilla , Chest Hunt Solution, Tinalphos, Tinalphos-Methyl, Chinometryat, Chinomethionate, Kiraraxil, Chitosan, Clobenazone, Clomethoxyphene, Chlorolose, Chloramben, Chloramine Phosphorus, Chloramphenicol, Chloraniforman, Chloranyl, Chloranokryl Chlorantraniliplol, Chlorazihop, Chlorazine, Chlorbenside, Chlorbenzurone, Chlorbicylene, Chlorbromron, Chlorbfam, Chlordan, Chlordecon, Chlordimeholm, Chlorlempentrin, Chlorethaseto, Chloretaseton, Chloroform Chloreturone, Chlorphenac, Chlorphenapir, Chlorphenazole, Florphenetol, Chlorphenidim, Chlorphenprop, Chlorfenson, Chlorphensulfide, Chlorfenbinphos, Chlorfenbinphos-methyl, Chlorfluazuron, Chlorfluazole , Chlorfluecol, Chlorflurene, Chlorfluenol, Chloridazone, Chlorimron, Chlorinate, Chlor-IPC, Chlormephos, Chlormequato, Chlormesron, Chlormethoxynyl, Chlornidin, Chlornitrophen, Chloroacetate, Chlorobenzylate, Chlorodinitronaphthalene, Chlorophenison, Chloroform, chloromebuform, chloromethiulone, chloroneb, chlorofacinone, chlorophos, chloropicrin, chloropon, chloropropilate, chlorotalonyl, chlorotorlon, chloroxifenidium, chloroxron, chloroxynyl, chlorhonium, chlorphoxim, chloroprazophos, chloroprocarb, chloroprofam, Chlorpyriphos, Chlorpyriphos-Methyl, Chlorquinox, Chlorsulfuron, Chlortal, Chlortiamide, Chlorthiophos, Chlortorlon, Closolinate, Kurtosan, Cholecalciferol, Choline Chloride, Chromaphenozide, Cycloheximide, Simectacarb, Cimetacarb, Cineline I, Cineline II, Cineline II Ethyl, symmethyrine, synosulfone, cintophen, siobutide, cisanilide, cismethrin, classifos, clefoxydim, clempirin, clenpyrin, cretojim, limbazole, chloroformate , Clozinahop, Chloetocarb, Crophenceto, Clophenotan, Clofentedin, Clofenbinfoss, Clofibric acid, Clohop, Chromazone, Chromeprop, Chronitralide, Cloprop, Chloproxim, Clopyralid, Croquintoset, Chloranthrum, Crosantel, Crotianidin, Closant. Trimazole, cloxyphonac, cloxylacon, clodilacon, CMA, CMMP, CMP, CMU, cordrelua, cholecalciferol, colohonate, copper-8-quinolinolate, copper acetate, copper acetohydrate, copper arsenate, basic copper carbonate, water Copper oxide, copper naphthenate, copper oleate, basic copper chloride, copper silicate, copper sulfate, basic copper sulfate, zinc copper chromate, coumacrol, kumafen, kumafos, kumafuryl, kumaphos, kumatetralyl , Cumethoxystrobin, cumitoate, spumoxystrobin, CPMC, CPMF, CPPC, credazine, cresol, cresylic acid, crimidin, crotamitone, crotoxyphos, crotoxyphos, kuhomet, cryolite, culua, kufuraneb , Cumylron, cuprovam, cuprous oxide, curcumenol, CVMP, cyanamide, cyanatrin, cyanazine, cyanophenphos, cyan, cyanophos, cyanotoate, cyantranliprol, cyanulic acid, siazofamide, cibutrin, cyclafuramide, cyclanilide, cyclaniliprol , Cycretoline, Cycloate, Licroheximide, Cycloplate, Cycloprothrin, Cyclopyrimolate, Cyclosulfamron, Cycloxidim, Cyclurone, Sienopyraphen, Siflufenamide, Siflumethofen, Siflutrin, Sihalohope, Sihalothrin, Sihexatin, Simiazol, Simoxanyl, Ciometrinyl Cipermethrin, Cipelcoat, Ciphenothrin, Cyprazine, Siprazole, Ciproconazole, Ciprodinyl, Ciprofulum, Cipromid, Ciprosulfamide, Siromadin, Cithioate, Citrex, Dimuron, Dalapon, Daminozide, Dayoton, Dazomet, DBCP, dd-Camper, DCB, DCIP, DCPA, DCPTA, DCU, DDD, DDPP, DDT, DDVP, Devacarb, Decafentin, Decamethrin, De Carbofuran, DEET, Dehydroacetic Acid, Diquat, Delacor, Delnab, Deltamethrin, Demefion, Demefion-O, Demefion-S, Demeton, Demeton-Me
Chill, Demeton-O, Demeton-O-Methyl, Demeton-S, Demeton-S-Methyl, Demeton-S-Methyl Sulfone (methyl sulfone), Demeton-S-Methyl Sulfone (methyl sulfone), DEP, Deparetrin, Delice, Dichloromethane , Desmethylin, desmethrine, d-fansilk Ebbingjuzuhi, diafentiurone, dialihol, dialiphos, diate, diamidaphos, dianato, diatomaceous soil (diatomaceous earth) diatomite Dibutyl, dibutyl succinate, dicamba, dicapton, diclobenyl, diclofenthion, diclofluanide, dicron, dichlorophalurea, dichlorobenzulone, dichlorophenidimu, dichlorfurrecole, dichlorofluenol, dichlormate, dichloromid, dichloromethane, dichloromeso Thiaz, Dichlorophene, Dichloroprop, Dichlorprop-P, Dichlorovos, Dichlorozolin, Dichlorozoline, Diclobutrazole, Dichlorosimet, Difluorohop, Dichromedin, Dichloroslam, Dicloslam, Diclohole, Dichlorofan, Dichromol Dicoumarol), Dicresyl, Dichlorotophos, Dichloro, Dichlorol, Dicyclanil, Dicyclonone, Dierdrine, Dienochlor, Dietumcoat, Dietatyl, Dietion, Dietithion, Dietionate, Dietofencarbate, Dietofencarbate , Diphenacomum, diphenoconazole, diphenopenten, diphenoxlon, diphenzoquat, diphethialone, difluorovidazine, diflubenzurone, difluphenican, difluphenicanyl, diflufenzopill, diflumethrim, dikeglac, diroll, dimethif, dimethyldimethyl, Dimepiperate, Dimetacron, Dimethane, Dimetacarb, Dimethacron, Dimethacrol, Dimetamethrin, Dimethenamide, Dimetenamide-P, Dimethipin, Dimethyrimol, Dimethate, Dimethmorph, Dimethrin, Dimethylcarbate, Dichloromethane, Dimethyl phthalate Methyl, dimethylbinphos, dimethyrane, dimexano, dimidazone, dymoxystrobin, gympylate, gymron, ginex, gingegenezuo, diniconazole, diniconazole-M, dinitramine, dinitrophenols, dinobutone, dinocup, dinocup-4, dinocup-6, dinocton , Dinophenate, Dinopenton, Dinoprop, Dinosam, Dinoseb, Dinosulfone, Dynotefuran, Dinotelb, Dinotelbon, Diophenolan, Dioxabenzophos, Dioxacarb, Dioxation, Dioxation, Diffacin (Diphenylamide), diphenylsulfone, diphenylamine, diphenylsulfide, diprogluic acid, dipropalin, dipropetrin, diptelex, dipimethitron, dipyrityion, diquat, disodium tetraborate, disosultap, disparua, dissgran, disul, disulfyllam, disulphoton, ditalimphos Dithiclophos, dithioether, dithiomethone, dithiopill, diuron, dixanthogen, d-limonene, DMDS, DMPA, DNOC, dodemorph, dodisin, dodin, dophenapine, doguadin, dominicala, dramectin, DPC, dorazoxorone, DSMA, d-trans-allethrin, d-trans-allethrin, zufurin, gymron, EBEP, EBP, ebphos, ecdysterone, ecromezol, EDB, EDC, EDDP, edifenphos, egrinazine, emamectin, EMPC, empentrin, enadenine, endosulfan, endal, endal ), Endothione, Endrin, Enestrovrin, Enilconazole, Enoxastrobin, Efilsulfonate, EPN, Epocholeon, Epophenonene, Epoxyconazole, Eprinomectin, Apronaz, EPTC, Elbon, Ergocalciferol, Elludixian Kaoan, S. Depalethrin, Esphenvalerate, ESP, Esprocarb, Etaceracil, Etaconazole, Etaphos, Etem, Etaboxam, Etachlor, Etalflularin, Etametosulfron, Etaprochlor, Etephone, Echidyllon, Ethiophee Ncarb, Ethiolate, Ethion, Ethiodin, Etiprol, Echimol, Etoate-Methyl, Etobenzanide, Etophmesate, Etohexadiol, Etoprop, Etoprophos, ethoxyphen, ethoxykin, ethoxysulflon, Ethyl clozet, Ethyl formate, Ethyl pyrophosphate, Ethylan, Ethyl- DDD, ethylene, ethylene dibromide, ethylene dichloride, ethylene oxide, etilicin, ethyl mercury 2,3-dihydroxypropyl mercaptide, ethyl mercury acetate, ethyl mercury bromide, ethyl mercury chloride, ethyl mercury phosphate, ethinophen, ETM, Ethinopromid, etobenzanide, etofenprox, etoxazole, etridiazol, etrimphos, etrimphos, eugenol, EXD, famoxadon, famufur, phenac, phenamidon, phenaminosulf, phenaminestrobin Flor, phenazakin, fenbuconazole, fenbutatin oxide, fenchlorazole, fenchlorphos, phenoclophos, fenchlorim, phenetacarb, fenfluthrin, fenfurum, fenhexamide, phenidine, phenitropan, phenothiolion, phenison, fenjuntong, phenocarb , Phenorobo, Phenoprop, Phenothiocarb, Phenoxacrim, Phenoxanyl, Phenoxaprop, Phenoxaprop-P, Phenoxasulfone, Phenoxycarb, Fempicronyl, Fempirithrin, Fenpropatrin, Fempropidine, Femppropimorph, Fempyrazamine , Fempiroxamate, Fenquinotrione, Fenridazone, Fenson, Fensulfothione, Fenteracol, Fentiaprop, Fention, Fention-Ethyl, Fentiaprop, Fentin, Fentrazamide, Fentrifanyl, Phenuron, Phenuron-TCA, Fenvalerate, Felbam, ferlimzone, ferric phosphate, iron sulfate, fipronyl, flam prop, flam prop-M, frazasulfone, flokumaphen, fromotkin, flonicamide, floraslam, fluaclipirim, fluazihop, fluazihop-P, fluazinum, fluazolate, fluazlon, flubenzidamide , Fulben Dimin, flubrocitrinate, flucarbazone, flucetosulfone, fluchloralin, flucoflon, flucycloxuron, flucitrinate, fludioxonyl, fluenethyl, fluenetil, fluenesulfone, fluphenacet, fluphenerim, fluphenican, fluphenican Phenoxlon, fluphenoxystrobin, flufenprox, flufenpill, flufendin, flufiprol, fluhexaphone, flumethrin, flumethbel, flumethrin, flumethoslam, flumedin, flumicrolac, flumioxazine, flumipropine, flumorph, fluometurone, fluopicolide, fluopyroid , Fluoridamide, Fluoroacetamide, Fluoroacetic acid, Fluorochloridone, Fluorodiphen, Fluoroglycophen, Fluorimide, Fluoramide, Fluoromidin, Fluoronitrophen, Fluoroxypyr, Fluorothrin, Fluotrimazole, Fluoxazobin, Flupoxam , Flupropacil, flupropazine, flupropanate, flupyraziflon, flupyrusulfone, fluconazole, flulalanel, fluconazole, fluconazole, flulenol, flulidon, flulocloridone, fluromidine, fluloxypill, fluluprimidol, fluluslamide, flulucamon, flusilazole Tenzine, fluthiaset, fluthamide, fluthianyl, flutranyl, flutriahole, fluvalinate, fluxazopyroxad, fluxophenim, holpel, holpet, homesaphen, honophos, horamsflufuron, forchlorphenuron, formaldehyde, formethanate, formothion, formaparanate, Hosamine, Josetil, Hosmethylan, Hospirate, Hostiazeto, Hostietan, Frontalin, Phtalide, Huberidazole, Fukaozin, Fukaomi, Fujunmanchi, Fulmi, Fumaline, Funaihekaolin, Fufenthiourea, Flalan, Flaluxil, Flametrin Fluconazole, fluconazole-cis, fresulin, furfural, frillazole, flumecyclox, flofanate, fryloxyphene, γ-BHC, γ-cyhalothrin, γ-HCH, genit Glyphosinate, griseofulvin, griseofulvin, glyphosinate, glufosinate, glufosinate-P, gliosinate, glyoxime, glyphosate, griseofulvin, gosipurua, grandlua, griseofulvin, guanoctin, guazatin, haraclinate, halauxifene, Halfenprox, halophenozide, halosafene, halosufflon, haloxidine, haloxihop, haloxihop-P, haloxihop-R, HCA, HCB, HCH, hemel, hempa, HEOD, heptachlor, heptaflusulin, heptenophos, heptargyl, harbimycin, harbimycin A, Heterophos, Hexachlor, Hexachlorolane, Hexachloroacetone, Hexachlorobenzene, Hexachlorobutadiene, Hexachlorophen, Hexaconazole, Hexaflumuron, Hexafluolamine, Hexaflulate, Hekirua, Hexamide, Hexadinone, Hexilthiophos, Hexithiazox, HHDN, horosulf, homobrushnoride, fankaiwo, fanchontin, fankaolin, fanchunzo, hydramethylnone, hydrargafene, slaked lime, hydrogen cyanamide, hydrogen cyanide, hydroprene, hydroxyisoxazole, himexazole, hikincarb, IAA, IBA , IBP, Icardin, Imazalil, Imazametabens, Imazamox, Imazapic, Imazapill, Imazakin, Imazetapill, Imazosulfuron, Imibenkonazole, Imiciaphos, Imidacloprid, Imidacrotis, Imidacrotis, Iminoctadine, Imiprosulin , Iodobonil, Iodocarb, Iodophenofos, Iodomethane, Iodosulfone, Iofensulfron, Ioxinyl, Ipadin, IPC, Ipconazole, Ipphencarbazone, Ipfentrifluconazole, Iprogenphos, Iprodion, Iprovaricarb, Iprimidum, Ipsedinol , IPSP, IPX, Isamidophos, Isazophos, Isobenzane, Isocarbamide, Isocarbamide, Isocarbhos, Isosyl, Isodrine, Isophenphos, Isophenphos-methyl, Isophytamide, Isolan, Isomethiodin, Iso Norlon, Isopanphos, Isopolynate, Isoprocalve, Isoprocil, Isopropalin, Isopropazole, Isoprothiolan, Isoproturon, Isopyrazam, Isopyri
Mole, isothiate, isothianol, isouron, isovalesion, isoxaben, isoxachlortol, isoxadiphen, isoxaflutor, isoxapyrihop, isoxathione, islon, ibermectin, isoxaban, izopamphos, izopamphos, izopamphos, , Jasmorin I, Jasmorin II, jasmonic acid, diaphanchonzon, diajizenxiaolin, diashanjunji, jiekaowan, jiekakushi, ginganmycin A, iodofenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III, Cadethrin, κ-bifenthrin, κ-tefluthrin, carbutyrate, caletazan, kasgamycin, kejunrin, kelevan, ketospiradox, diatomaceous soil, kinetin, quinoprene, kiraraxil, cresoxime-methyl, quicaoxy, lactophene, λ-sihalothrin, lactophene, lead Lenacil, Repimectin, Lepthos, Ryanbentinzi, Lime-Sulfur Mixture, Lindan, Lineatin, Linuron, Lilimhos, Littlea, Lufenuron, Lufenuron, Luxian Kaolin, Lubzing Junshi, Luvhumichuvzi, Luvsian Kaolin , Lithidathiol, M-74, M-81, MAA, Magnesium Phosphate, Malathion, Mardison, Hydrazide Maleate, Maronoben, Maltodextrin, MAMA, Mancopper, Mancozeb, Mandestrobin, Mandipropamide, Maneb, Matrin, Magidox, MCC , MCP, MCPA, MCPA-thioethyl, MCPB, MCPP, mebenyl, mecarbum, mecarbindide, mecarphone, mecoprop, mecoprop-P, medimeform, medinotelb, medolua, mephenacet, mephenoxam, mefenpil, mefluidide, megatomoic acid, melysil alcohol MEMC, Menazone, MEP, Mepanipirim, Meperfluthrin, Mephenate, Mephosphoran, Mepicat, Mepronil, Meptyrdinocup, Mercaptodimetul, Mercaptophos, Mercaptophosthiol, Mercurytothione, Tertiary mercury chloride, Mercury oxide, Mercury chloride, Melphos, Melphos Oxide, Mesoprazine, Mesolufuron, Mesotrione, Mesulfen, Mesulfenphos, Mesulfen, Metacresol, Metaflumison, Metalaxil , Metalaxil-M, Metaaldehyde, Metam, Metamihop, Metamitron, Metaphos, Metaxone, Metazachlor, Metazosulfone, Metazocosolone, Metoconazole, Metepa, Metofrazone, Metabenzthiazulone, Methachos, Metalpropalin, Metam, Metamidphos, Metasulfocarb , Metazol, methofloxam, methibensulone, methidathione, methionenecarb, methiocarb, methipylisulfuron, methiotepa, methiozoline, methiulone, methocrothos, metholcarb, methometon, methmil, methoprene, methylmethophosphoryne , methoxychlor, methoxyfenozide, Methoxyphenone, methyl Aho acrylate, bromide Mechirubu, methyl eugenol, methyl iodide, methyl isothiocyanate, methyl parathion, methyl acetoacetate phosphite, methyl chloroform, methyl dithiocarbamate, Mechirujimuron, methylene chloride, methyl - isofenphos, Methyl mercaptophos, Methyl mercaptophos oxide, Methyl mercaptophosthiol, Methyl mercury benzoate, Methyl mercury dicyandiamide, Methyl mercury pentachlorophenoxide, Methyl neodecanamid, Methyl nitrophos, Methyl triazothione, Methylozoline, Methylam, Methylam- Zinc, Metbenzlon, Metbromron, Metoflutrin, Methylchlor, Methylcarb, Methylmethurone, Metminostrobin, Metoslam, Methyloxadiazone, Methyloxlon, Methylphenone, Methylam, Methylbuzin, Methylhonate, Methylphosulmethone, Methylphosulfone, Methylphosulfone , Miesuan, Miewenchuzi, Milbemectin, Milbemycin oxime, Milneb, Mima 2 Nan, Mipahox, MIPC, Millex, MNAF, Mogchun, Molinate, Morosultap, Monfluorotrin, Monalide, Monisron, Monoamitraz, Monochloracetic acid, Monochloroacetic acid, Monochrometophos, Monolinuron, Monomehipo, Monosulfiram, Monosulfuron, Monosul Tap, Monuron, Monuron-TCA, Morphanquat, Moroxydin, Morphothione, Morzide, Moxidectin, MPMC, MSMA, MTMC, Muscarua, Microbutanyl, Microzoline, Millicyl alcohol, N- (ethylmercury) -p-toluenesulfonanilide, NAA, NAAm, Nabam, Naphthalofos, Nared, Naphthalene, Naphthaleneacetamide, Naphthalic acid anhydride, Naphthalophos, Naftoxyacetic acid, Naftylacetic acid, naphthylindan-1,3-dione, naphthyloxyacetic acid, naproanilide, napropamide, napropamide-M, naptalum, natamicin, NBPOS, nebuurea, nebron, nendrin, neonicotine, nichlorphos, niclophen, nicrosamide, nicobiphen, nicosulfone, Nicotin, nicotine sulfate, nifluridide, nicomycin, NIP, nipyraclophen, nipyralofene, nitempyram, nithiadin, nitraline, nitrapyrin, nitrilacalve, nitrophen, nitrofluofen, nitrostyrene, nitrotal-isopropyl, nobormid, nonanol, norvomid, norea, norfrazone, nornicotin, Norlon, Novallon, Noviflumuron, NPA, Nuarimol, Nuranon, OCH, Octachlorodipropyl ether, Octinone, o-dichlorobenzene, Offrace, Omethoate, o-phenylphenol, Orbencarb, Orfuralua, Orthobencarb, Ortho-dichlorobenzene, Orthoflufamron, orictalua, orisastrobin, oryzarin, ostol, ostole, ostramone, obatron, obex, oxabetrinyl, oxadialzil, oxadiazone, oxadixyl, oxamate, oxamil, oxapyrazon, oxapyrazon. Flufuron, oxathiapiproline, oxadichromefone, oxine-copper, oxine-Cu, oxophosphate, oxpoconazole, oxycarboxyne, oxydemethone-methyl, oxydeprophos, oxydisulfoton, oxyenadenine, oxyfluorphen, oxymatrin , Oxytetracycline, Oxythioquinox, PAC, Paclobutrazole, Pyconzine, Paletrin, PAP, Para-dichlorobenzene, Paraflulon, Paracoat, Parathion, Palatin-Methyl, Parinol, Paris Green, PCNB, PCP, PCP-Na, p-dichlorobenzene, PDJ, pebray To, peginex, pefrazoate, pelargonic acid, penconazole, pencyclon, pendimethalin, penphenate, penfluphen, penflulon, penoxalin, penoxstam, pentachlorophenol, pentachlorophenyllaurate, pentanochlor, penthiopyrado, pentomethrin, pentoxazone, parkoldecon, perfluidone, Permethrin, pesoxamide, PHC, phenamacryl, phenamacryl-ethyl, phenaminosulf, phenazineoxide, phenetacarb, phenisobum, fencapton, phenmedifam, fenmedifam-ethyl, phenobenzlone, phenothiol, phenothrin, fenproxide, fentoate, phenyl Mercury Urea, Phenylmercury Acetate, Phenylmercury Chloride, Phenylmercury Derivatives of Pyrocatechol, Phenylmercury Nitrate, Phenylmercury Salicylate, Holate, Hosacetim, Hosalon, Hosametin, Hosazetim, Hosazetin, Phoscyclotin, Phosdiphen, Josetil, Phosphorane, Phosphoran-Methyl, Hosglycine, Hosmet, Phsnicrol, Phosphamide, Phsphamidene, Phosphine, Phosphinotricin, Hoffhocarb, Phosphorus, Hostin, Hoxim, Hoxim-Methyl, Phtylide, Phenylphos, Phenylthrin, Picarbutrazox, Picardine, Picrolam, Picolinafene, Picoxystrobin , Pimalucin, Pindon, Pinoxaden, Piperlin, Piperazine, Piperonylbutoxide, Piperonylcyclonene, Piperophos, Pyrottanyl, Piprotanyl, Pyprotal, Pyrimetaphos, Pyrimicalbu, Pyriminyl, Pyrimioxyphos, Pyrimiphos-ethyl, Pyrimiphos-methyl, Pival, Pivaldione PMA, PMP, polybutenes, polycarbamate, polychlorcampene, polyethoxyquinoline, polyoxin D, polyoxins, polyoxolim, polythiaran, potassium phosphite, potassium azide, potassium cyanate, potassium ethylxanthogenate, potassium naphthenate, Potassium polysulfide, potassium thiosocyanate, pp'-DDT, praretrin, plecosene I, plecosene II, plecosene III, pretilachlor, pyrimidophos, pyrimisulfuron, provenazole, prochloraz, procronol, prussidine, procymidone, prodiamine, profenophos, proflu Psoralen, proflularin, profluthrin, prohoxydim, proflulite-aminium, proglinazine, prohexadione, prohydrojasmon, promacyl, promecarb, promethone, promethrin, promethrin, promethrin, promethrine, promlyt, promipazole, propamyl , Propamocarb, Propanyl, Propaphos, Propaxahop, Propargit, Propatrin, Propazine, Propetanphos, Propham, Propiconazole, Propidin, Propineb, Propisochlor, Propoxul, Propoxycarbazone, Propylisome, Propyrisulfuron, Propizzamid, Proquinadide Prothrel, prosulfalin, prosulfocalve, prosulfone, protidethione, prothiocarb, prothioconazole, prothiophos, protoate, protriphenbute, proxan, pyrimidophos, pyrinachlor, psoralen, psoralene, psoralene, psoralene, Pymetrodin, pyracarbolide, pyracrophos, pyracronyl, pyracrostrobin, pyraflufen, pyrafluprol, pyramat, pyrametostrobin, pyraoxystrobin, pyrasulfotor, pyraziflumid, pyrazolate, pyrazolinete, pyrazono, pyrazophos, pyrazosulfuron, pyrazothione, pyrazoxifene, pyrethrolen , Pyrethrin I, Pyrethrin II, Pyrethrins, Pyribambends-isopropyl, Pyribamubenz-propyl, Pyribenecarb, Pyrbenzoxim, Pyribuchicarb, Pycrol, Pyridaben, Pyridahole, Pyridaryl, Pyridaphenthion, Pyridaphenthion, Pyridaphenothion, Pyridaphenh Pyriphthalide, Pyrimetaphos, Pyrimetanol, Pyrimicalve, Pyrimidiphen, Pyriminobac, Pyriminostrobin, Pyrimiphos-ethyl, Pyrimiphos-Methyl, Pyrimisulfane, Pyrimitate, Pyrinurone, Pyriophenone, Pyriprol, Pyrypropanol, Pyriproxyfen, Pyrisoxazole, Pyritiovac, Pyrrolianth, Pyroquilone, Pyroxasulfone, Pyrox slam, Pyroxicrol, Pyroxiflu, Kinkaosuan, Ki Ngkling, quasiah, quinacetor, quinalphos, quinalphos-methyl, quinazamide, quinchlorac, quinconazole, kimmerak, quinocramine, quinomethionate, quino
Namide, Kinothione, Kinoxyphene, Kinthiophos, Kintozen, Kizarohop, Kizarohop-P, Quench, Quingzing, Labenzazol, Lahoxanide, R-Diniconazole, Levemid, Reglon, Renriduron, Rescala, Resmethrin, Rodetanyl, Rhodojaponin-III , R-Metalaxil, Rodetanyl, Ronell, Rotenon, Lania, Sabadira, Safflephenacyl, Saijunmao, Saicentong, Salicylanilide, Sarifluofen, Sanguinaline, Santonin, S-bioaletrin, Scladan, Scilyloxide, Sebutyrazin, , Sesamex, Sesamolin, Seson, Setoxydim, Sevin, Shangsia ankaolin, Shungudianan kaolin, S-hydroprene, Siduron, Sifmichuvzi, Sigurua, Silafluofen, Silatran, Silica erogel, Silica, Siltiofam, Silthiofam ), Sylthiophan, Sylvex, Simazine, Simeconazole, Simetone, Simetrin, Simetrine, Syntophen, S-quinoprene, Slime, SMA, S-methoprene, S-methacrol, Sodium hydride, Sodium azide, Sodium chlorate, sodium cyanide, sodium fluoride, sodium fluoroacetate, sodium hexafluorosilicate, sodium naphthenate, sodium o-phenylphenoxide, sodium orthophenylphenoxide, sodium pentachlorophenate, sodium pentachlorophenoxide, polysulfide Sodium, sodium fluorinated, sodium tetrathiocarbonate, sodium thiocyanate, solan, sofamid, spiteram, spinosado, spirodiclophen, spiromethifene, spirotetramato, spiroxamine, stylophos, streptomycin, strikinine, sulcatol, sulcofluone, sulcotrione, Sulfate, sulfentrazone, sulfylum, sulfuramide, sulfodazole, sulfomethulone, sulfosate, sulfosulfone, sulfotep, sulfotepp, sulfoxaflor, sulfoxide, sulfoxime, sulfate Yellow, sulfuric acid, sulfryl fluoride, sulglycapine, sulfosate, sulprophos, sultropen, swep, τ-fluvalinate, tablon, tagimcarb, TBTO, TBZ, TCA, TCBA, TCMTB, TCNB, TDE, tebuconazole, tebufenozide, tebufenozide, tebufenozide, tebufenozide, tebufenozide , Tebutam, Temchiuron, Tecrophthalam, Technazen, Tecolum, Tedion, Teflubenzron, Tefurthrin, Tefriltrion, Tembotrion, Temefos, Temefos, Tepa, TEPP, Tepraloxidim, Teproloxidim, Terraleter Crawl, terbuphos, terbumeton, tergutyrazine, terbutor, terbutrin, terbutrine, terramicin, terramycin, tetocyclasis, tetrachloroethane, tetrachlorobinphos, tetraconazole, tetra , Tetramethrin, tetramethrin, tetramethylfurthrin, tetramine, tetranactin, tetraniliprol, tetrapion, tetrasul, thallium sulfate, thallium sulfate, temefos roll, θ-cypermethrin, thiabendazole, thiacloprid Thiadifluol, thiamethoxam, thiamethurone, thiapronil, thiazaflulon, thiazflulon, thiazone, thiazopyr, temefos, temefos, tidiadimin, tidiazulone, thiencarbazone, thifensulfuron, tifluzamide, thimerosal, chimet, thiobencarb, thiocarboxyl ), Thiochlorphenphime, thiochanatodinitrobenzene, thiocyclam, thiodan, thiodiazol-copper, thiodicalve, thiofanocalb, thiophanox, thiofluoxymart, thiohenpa, thiomersal, thiomethon, thionaten, thiophanate, thiophanate-ethyl, thiophanate. -Methyl, thiophos, thioquinox, thiosemicarbazide, thiosultap, thiotepa, tioxamil, tiram, thiuram, Turingiencin, thiabendazole, thiazinyl, thiaphenacyl, thiaothian, TIBA, tifator, thiocarbadyl, thiochlorolim, thioxazaphene, thioxymid, tyrpate, TMTD, turquophos-methyl, tolfenpyrado, tolprocarb, tolpralate, trifluanide, tolylfluanide, trilmethane Toxaphene, TPN, tralcoxydim, tralocitrin, tralomethrin, traropyryl, transfluthrin, transpermethrin, tretamine, triacontanol, triazimehon, triazimenol, triafamon, triarate, tri-alate, triamiphos, triapentenol, trilatin, tri Alimol, triasulfuron, triazamate, triazbutyl, triaziflam, triazophos, triazothione, triazoxide, tribasic copper chloride, acid-basic copper sulphate, tribenurone, tribuphos, tributyltin oxide, tricamba, tricramide, triclopil, trichlorfon, trichlormethaphos-3 , Trichloronat, trichloronate, trichlorotrinitrobenzene, trichlorfon, triclopil, triclopyricalbu, tricresol, tricyclazole, tricyclohexyltin hydroxide, tridemorph, tridiphan, trietazine, triphenmorph, triphenophos, Trifloxystrobin, trifloxyflufuron, trifludimoxazine, triflumesopirim ,, triflumizole, triflumuron, triflularin, triflusulfone, trihop, trihopsime, triphorin, trihydroxytriazine, trimedrua, trimetacarb, trimethurone, trinexapac, Triphenyltin, tryplene, tripropindan, tryptride, tritac, trithialan, triticonazole, tritosulfone, trunkcol, zoyerin, uniconazole, uniconazole-P, arborside, uredepa, valerate, baridamycin, baridamycin A, burr Fenalate, Baron, Bamidethione, Vanguard, Vaniliprol, Vernolate, Bincrozoline, Vitamin D3, Warfarin, Xiaocheonryulin, Shinchuan, Shiwochunan, Shiwochunzi, XMC, Xylacro Lu, xylenols, xylylcarb, ximiazole, isidine, zarylamide, zeatin, zenciaoan, zenciaolin, ζ-cypermethrin, zinc naphthenate, zinc phosphide, thiazole zinc, thiazole zinc, trichlorophenolic acid, trichlorophenoxide Zinc, Zineb, Dilam, Zoraprophos, Zukmarin, Zoxamide, Zoanchunzi, Zokaoan, Zochunzi, Zumifanglong, α-Chlorohydrin, α-Exdison, α-Multistriatin, α-naphthylacetic acids, and β- Exdison,
(2) The following compounds

(3) A compound known as Rotilaner having the following structure

;as well as
(4) Compounds in the table below

.. The active ingredient

The pesticide composition according to claim 5, wherein the pesticide composition is selected from the group consisting of 1,3-dichloropropene, chlorpyrifos, chlorpyrifos-methyl, hexaflumuron, methoxyphenozide, nobiflumuron, spinetram, spinosad, sulfoxaflor, and sulfuryl fluoride. A pesticide composition comprising the compound according to any one of claims 1, 2, 3, or 4, further comprising a MoA substance meaning a substance having a mechanism of action selected from the following.
(1) Acetylcholinesterase (AChE) inhibitor,
(2) GABAergic chloride channel antagonist,
(3) Sodium channel modulator,
(4) Nicotinic acetylcholine receptor (nAChR) agonist,
(5) Nicotinic acetylcholine receptor (nAChR) allosteric activator,
(6) Chloride channel activator,
(7) Juvenile hormone imitation,
(8) Various non-specific (multisite) inhibitors,
(9) Modulator of the string organ,
(10) Tick growth inhibitor,
(11) Insect midgut membrane microbial disturber,
(12) Mitochondrial ATP synthase inhibitor,
(13) Decoupling agent for oxidative phosphorylation through disturbance of proton gradient,
(14) Nicotinic acetylcholine receptor (nAChR) channel blocker,
(15) Chitin biosynthesis inhibitor, type 0,

(16) Chitin biosynthesis inhibitor, type 1,
(17) Diptera molting disturber,
(18) Ecdysone receptor agonist,
(19) Octopamine receptor agonist,
(20) Mitochondrial complex III electron transfer inhibitor,
(21) Mitochondrial complex I electron transfer inhibitor,
(22) Voltage-gated sodium channel blocker,
(23) Acetyl-CoA carboxylase inhibitor,
(24) Mitochondrial complex IV electron transfer inhibitor,
(25) Mitochondrial complex II electron transfer inhibitor and
(28) Ryanodine receptor modulator . The pesticide composition according to claim 8 , wherein the MoA substances are from the MoA substance group alpha (MoAMGA), which collectively means the following substances.
Abamectin, acephate, acequinosyl, acetamipride, acrinathrin, aranicalve, aldicarb, allethrin, α-cypermethrin, aluminum phosphate, amitraz, azamethifos, azinephos-ethyl, azinephos-methyl, azocyclotin, benziocarb, benfracarb, benzulfruthrin, β- -Cypermethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenylisomer, bioallethrin, bistriflulon, bolux, buprofezin, buttocarboxym, butoxycarboxym, kazusaphos, calcium phosphate, carbalyl, carbofuran, carbosulfane, cartap hydrochloride, Chlorpyrifos, chlordan, chlorethoxyphos, chlorphenapir, chlorphenbinphos, chlorfluathrin, chlormephos, chloropicrin, chloropyrifos, chlorpyrifos-methyl, chromafenozide, clofenthedin, clothianidin, kumaphos, cyanide, cyanophos, Cyantraniliprol, cycloprothrin, cyenopyraphen, cyfluthrin, cypermethrin, cypermethrin, cypermethrin, cypermethrin, cypermethrin, cilomadin, d-cis-trans-allethrin, DDT, deltamethrin, demethon-S-methyl, diaphenthiron, Diazinone, dichlorvos / DDVP, dichlorpyrifos, difluorovidazine, diflubenzlone, dimethate, dimethylbinphos, dinotefuran, disulphoton, DNOC, d-trans-allethrin, emamectin benzoate, empentrin, endosulfane, EPN, esphenvalerate, ethiophencarb , Etofenprox, etoxazole, famfur, phenamiphos, phenazakin, fenbutatin oxide, fenitrothione, phenocarb, phenoxycarb, phenpropathrin, phenpyroxymate, fenthion, fenvalerate, fronicamid, fluacripirim, flubenzidamide, flucycloxlone, flucitrinate Phenoxron, flumethrin, flupyraziflon, formanate, hostizet, fratiocarb, γ-cypermethrin, halphenprox, halophenozide, heptenophos, hexaflumron, hexithiazox, hydramethylnone, hydroprene, imi Ciaphos, imidacloprid, imiprosulin, indoxacarb, isofenphos, isoprocalve, isoxathione, cadesulin, quinoprene, λ-cypermethrin, repimethrin, lurenuron, malathion, mecarbam, metaflumison, metamidphos, methiadation, methiocarb, methaminol ) Salicylate, methoxychlor, methoxyphenozide, methyl bromide, metorcarbe, mevinphos, milbemectin, monochromotophos, naredo, nicotine, nitempirum, novallon, nobiflumron, oxamil, oxydemethrin-methyl, palatine, palatine-methyl, permethrin, phenothrin, fentoate , Hosalon, Hosmet, Phosphamiden, Hosphin, Hoxime, Pyrimicarb, Pyrimiphos-methyl, Paralesulin, Profenophos, Propargit, Propetanphos, Propoxul, Prothiophos, Pymetrodin, Pyraclophos, Pyretrin, Pyridaben, Pyridafenthion, Pyrimidiphen , Silafluofen, spinnetram, spinosad, spirodiclofen, spiromesifen, spirotetramato, sulfurlamide, sulfotep, fluhoxaflor, sulfuryl fluoride, talisman, τ-fluvalinate, tebuphenozide, tebufenpyrado, tebupyrinphos, tefluthrin Temefos, terbuphos, tetrachlorobinphos, tetrediphon, tetramethrin, tetramethrin, θ-cypermethrin, thiacloprid, thiamethoxam, thiocyclam, thiodicalve, thiophanox, thiomethon, thiosultap-sodium, tolfenpyrad, tralomethrin, transfluthrin, triazamate, triazophos Triflumron, trimetacarb, bamidthione, XMC, xylylcarb, ζ-cypermethrin, and zinc phosphate . The weight ratio of the compound represented by the formula 1 to the active ingredient is 100: 1 to 1: 100, 50: 1 to 1:50, 20: 1 to 1:20, 10: 1 to 1: 10, 5: The first aspect of claim 5, 6, 7, 8, or 9, which is selected from 1 to 1: 5, 3: 1 to 1: 3, 2: 1 to 1: 2, and 1: 1. Agricultural chemical composition. A process for controlling pests, wherein the process applies a pesticide-effective amount of the compound according to any one of claims 1, 2, 3, or 4 to a place other than humans. Including the process. A pesticide-effective amount of a pesticide composition according to any one of claims 5, 6, 7, 8, 9, or 10, wherein the process controls pests in a place other than humans. The process, including applying. The pest is in or above a place other than humans, and the pest is
Ants, aphids, beetles, stains, cockroaches, crickets, grasshoppers, fleas, flies, grasshoppers, whiteflies, locusts (including fungus), locusts, mites, moths, nematodes, scale insects, komukade, termites, horse mackerel, ticks, spider bees, The process of claim 12, which is and / or a whitefly. A process comprising applying the compound according to claim 1, 2, 3, or 4 or the pesticide composition according to claim 5, 6, 7, 8, 9, or 10 to a seed. The compound according to any one of claims 1, 2, 3, or 4 is applied to a place other than humans including non-human animals in order to control endoparasites and / or ectoparasites. process.